Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd nonee C s13dmtyiiaoe2sln die,prasdet h aeo t rprto (see preparation its of ease commonly the most to The spacer. due aryl perhaps or 3.3). (dmise), Section an 1,3-dimethylimidazole-2-selone feature is often two 2) HCU (Figure the encountered group are chalcogenourea ring one this than five Flanking more usually well. with is as ring achieved The been nitrogen have group. each rings illus- functional N seven-membered and 1 HCU ring, and Figure the a six- possible. featuring within though variation architectures is membered, structural molecular atom considerable carbon common Te) is most Se, there the = substituent, trates (E organic E other = one C contains the atom wherein compounds, of class this Within HCUs cyclic of variety Structural 2 tellone selenone, or (selone tellurourea). chalcone (selenourea, include chalcogenourea examples and Popular tellurone) adopted. or universally being group term [3]. particular HCUs main of no including chemistry available, redox are the chemistry and 8] of [7, areas non-) substitution related (including full complexes on with and reviews rings, comprehensive featuring Many analogues nitrogen. tellurium and at feature only will as (i. contribution substituents such this NH HCUs featuring but acyclic cyclic of featuring are which studies review those many a are by There followed organo-substitution. described, less covered. be is will 2017 HCUs late cyclic to up of Literature chemistry. properties coordination physical their and preparation the sections, N on particular medicine in 2], [1, cus science ar- [4 material many in in biochemistry investigated applications and been to have chemistry [3], (HCUs) coordination chalcogenoureas and heavy structural fundamental These from decades. eas few last the in its attention and ing of analogues tellurium-containing and Selenium- Introduction 1 DOI: metals. d-block and p- het- with featuring chemistry chalcogenoureas Keywords: coordination heavy diverse cyclic This their of chemistry. explores preparation andmaterials and the their cores for asmedicine erocyclic to methods synthetic such due the fields attention in summarizes increasing chapter applications potential received and have reactivity ligands chemical carbene diverse N-heterocyclic of derivatives Chalcogenated 1 telluroureas and seleno- cyclic of chemistry coordination and Synthesis Ritch S. Jamie GRUYTER DE 08Wle eGutrGb,Berlin/Boston. GmbH, Gruyter de Walter 2018 © Ritch S. Jamie Abstract: eateto hmsr,TeUiest fWnie,55PraeAeu,Wnie,Mntb 3 E,Cnd,E-mail: Canada, 2E9, R3B Manitoba Winnipeg, Avenue, Portage 515 Winnipeg, of University The Chemistry, of Department [email protected] sbttet hc r sal h aegop huhaymti ainsaekon npriua,HCUs particular, In known. are variants asymmetric though group, same the usually are which -substituents In the following centres. nitrogen tertiary flanking feature which and ligands (NHC) carbene -heterocyclic tsol entdta hr r eea ae o hscaso opudt efudi h ieaue with literature, the in found be to compound of class this for names several are there that noted be should It featuring HCUs are as right, own its in developed well very course of is thioureas and of chemistry The 10.1515/psr-2017-0128 hloeora,ntoe eeoyls oriainchemistry coordination heterocycles, nitrogen chalcogenoureas, stecrepnigauthor. corresponding the is 1 cyclic – ] ag ubro opud alit hsdsicin n hscatrwl fo- will chapter this and distinction, this into fall compounds of number large A 6]. eeo n elrues hc r omlycacgndrvtvso h popular the of derivatives formally are which telluroureas, and seleno-

.iiaoiie2sln) opoieafcsdreview, focused a provide To imidazolidine-2-selone). e. N sbtttddrvtvshv eevdincreas- received have derivatives -substituted hsclSine eiw.21;20170128 2018; Reviews. Sciences Physical N,N dmtyslnue,or -dimethylselenourea, 1 Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd abns[0 ynal eae h elru eiaiewsrpre oetuetluimadrvr back revert and tellurium extrude R =Et)[16]. to [16]. thermolysis reported or was Te, photolysis derivative = ofstable, upon tellurium advent (E biimidazolidine The the the decade. to a predates atellurourea nearly method of by 0 the latter at [10] se- solution example Interestingly, (THF) well-characterized a toluene. tetrahydrofuran first form refluxing in the to required yield and high (2)) mation in [15], (eq. formed Ph) chalcogen derivative = elemental selenium R The with Se, react = to (E shown lenourea been have dimers) (carbene Biimidazolidines manner. telluroureas this 11], in [10, prepared 1990s were early [14] the selenoureas in need ligands subsequently the NHC then without stable chalco- and and of elemental 13] NHC, reports with [12, the after carbene Soon with the (1)). compatible solvent of (eq. any temperature reaction in elevate direct cleanly to a proceeding then generally facile, NHC, quite an is purchased gen or prepared already has one If chalcogenation Direct 3.1 prior these including not HCUs reviewed cyclic been to have routes precursors synthetic several carbene on prepare focus to will steps. routes section this numerous and The com- [9], these centre. thoroughly to chalcogen routes the synthetic of reported the most troduction and assembling ligands, by NHC begin of derivatives pounds considered be can HCUs Cyclic chalcogenoureas heavy of Synthesis 3 2: Figure 1: Figure 2 Ritch C opud ihmlil ucinlgroups. functional E = C multiple with compounds HCU group. functional E = C one with compounds HCU Common N htrcci ig i. ring, -heterocyclic

.a mdzlu riiaoiimsl,pirt in- to prior salt, imidazolinium or imidazolium an e.

C hl elrue for- tellurourea while °C, “ bottleable EGRUYTER DE (1) ” Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd infcn osi rdc il.Ti ehddtsbc o17,we twsfrtue to generateacyclic 1: Table used first was it when 1970, to back without dates conditions ambient method This under conducted [17]. yield. be thiourea inproduct sometimes but anhydrous can loss reactions toprogress, significant the a reaction and con- the strict anhydrous for less requires reflux are but requires requirements temperature, generally room carbonate at chalco- potassium cleanly elemental Methanolic proceeding ditions. powdered of advantage of the use has solvent alkoxide make as hindered K such protocols conditions methanolic encountered reaction either carbene other commonly and as the most well gen deprotonates as two used, base The source chalcogen The temperature. and 1). and base Table the in and vary (3). NHC methods These (eq. an source base, yield a chalcogen to with a salt precursor imidazolinium with or imidazolium reaction the concomitant of deprotonation and feature HCUs cyclic of preparations Most Deprotonation-chalcogenation 3.2 GRUYTER DE 3 2 6 5 4 1 Heterocycle Entry eetddeprotonation Selected – 2 nsitu in hloeainpooosfrcci eeo n telluroureas. and seleno- cyclic for protocols chalcogenation CO Se Se Se Na Se K Te or Se Na or source Chalcogen 2 2 3 Se Te ety1 rKO or 1) (entry hc hnrat ihtecacgnsuc ofr h eie HCU. desired the form to source chalcogen the with reacts then which , 2 2 none DBU NaN(SiMe KO Base KO 2 CO t t Bu Bu 3 t 3 ui H ety2 stebs/ovn ytm h s of use The system. base/solvent the as 2) (entry THF in Bu ) 2 neat 150 MeCN THF Et h 96 (Se), h 24 MeOH ovn Temperature, Solvent THF 2 O h days 75 overnight RT, (Te) )R,overnight RT, 2) min 1) time )KO 2) Na 1)

− C several °C,

C(W,1 (MW), °C 78 2 t E u 0h 10 Bu,

C 30 °C, 2 h; 8 , (81 (68 (91 (95 (61 (41 yield) (% Product – – – – %) %) 86 70 77 48

%) %) %) %) Ritch [56] [42] [72] [71] [41] [70] Reference (2) 3 Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd ocle n-o ytee obn h hloe diinse ihoeo oesesi h ytei fim- of synthesis the in steps more or one precursors, with imidazolinium step or addition idazolium chalcogen the combine syntheses one-pot So-called reactions One-pot 3.3 general the follow chalcones) Bis(benzimidazole instance. [22]. this (6)) in (eq. operating 3 is 16 entry (5), of in eq. conditions reaction in that this as from such pathway, obtained also was product the featuring study a ( In (4)). (eq. way this ( in ligands bis(selone) bridged Alkyl salts. iodide 6). or (entry bromide product selone imidazole the 30 need form (mp the to acetate without solvent 1-ethyl-3-methylimidazolium acceptor, of proton liquid absence the Another ionic 5). the as The (entry acting base. salt external irradiation imidazolium an microwave an for under of inacetonitrile anion the involves salt variation interesting triflate benzimidazolium explored a been of not selenylation has method this ( but temperature chalcogen, excess the eliminating unknown. is Se, scope for for its species, yields stand-in improve and carbenic a thoroughly to the as reported used with been naphthalene has been ratio strategy of 50 has equimolar to this presence an up Nonetheless, the by in excess. in systems twofold used THF some in when in present Additionally, chalcogen is [18]. the chalcogen catalyst of the donor reduction electron sodium an as as such additional procedure the a requires using This genide powders. as chalcogens elemental the Na of use The 4 n )bssln)lgn a oiebylwr(34 lower noticeably was ligand bis(selone) 2) = otbdnaecacgnue iad r rprduigtemto rmety1 sn bis(imidazolium) using 1, entry from method the using prepared are ligands chalcogenourea bidentate Most NaN(SiMe as such bases Strong Ritch 2 − E 78 2 at a enrpre sgvn ihryed o ezmdzl eiaie ety3,versus 3), (entry derivatives benzimidazole for yields higher giving as reported been has salts

C odtosaerqie.Teogncbs B a enrpre oefc high-yielding effect to reported been has DBU base organic The required. are conditions °C)

oprdt sn lmna hloe o oedfiuttasomtos Na transformations. difficult some for chalcogen elemental using to compared % nsitu in 3 ) n 2 o5sre,i a oe htteyedo h tyeebridged the of yield the that noted was it series, 5 to 2 = aebe tlzd(nr ) huhietamshr n low and atmosphere inert though 4), (entry utilized been have xmlso hssrtg nld h s of use the include strategy this of Examples .

ess53 versus %

il 6.Ti ugssta optn elimination competing a that suggests This [6]. yield % n n 1] n 2] 2] a esynthesized be can [21]) 5 [20], 4 and 3 [19], 2 and 1 = – 57 nsitu in

) iy-usiue ooeoeside monoselone vinyl-substituted A %). rprto ftesdu dichalco- sodium the of preparation

C ecswt eeimin selenium with reacts °C) N,N ’-disubstituted EGRUYTER DE 2 (4) (3) (6) (5) Se Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd tslu,floe ytetetwt oimhdoe eeie(q 1) 2] ylcslnue a also was NHC-CSe selenourea formal cyclic a A [29]. of operationally (11)) decomposition 11 and (eq. of thermal effective yield selenide during more hydrogen form be sodium to to with found reported treatment akylation involving was by selenoureas to followed method thioureas sulfur, acyclic This transforming reaction at [28]. of method via (10)) reported heterocycles previously (eq. a oxamide-type than base simpler yield and to chloride cyclized oxalyl been with have selenoureas acyclic Diorganosubstituted and specified) not solvent Bn; Me, 40 = and transformation 35 (R the between spectroscopy report, 2-Selenoether- one (NMR) 50 In and beenreported. resonance (9)). 40 between (eq. also magnetic occurred nitrogen have to nuclear selenium by isomer, from categories selenourea monitored group cyclic benzyl was the previous or the alkyl to the rearrangement into of thermal migration undergo fit via to not observed been do have imidazoles which substituted methods other few A methods Other 3.4 study. to study from varies which 1- not, are by alkylating or procedures isolated made is these product not alkylation or salt in1993, whether imidazolium inmethanolic 26]; the whether [25, reported refluxing on halides then benzyl first solvent, including was the substituent, off second dmise decanting HCU acetate, ethyl popular molecule K in benzimidazole the iodide or methyl example, imidazole with an For methylimidazole of HCUs. alkylation with yield chalcogenation to the combined have reports Other The (7)). form to (eq. selenium, backbone 39 with imidazoline reaction an bomb with sealed high-temperature selenoureas a in triethylorthoformate and diaminoethanes GRUYTER DE 2

CO ,btteohrdrvtvsafre ilsof85 yields afforded derivatives other the but %, 3 ntepeec fslnu e.() 2] te lcrpii abnsucscnb sdt ntl the install to used be can sources carbon electrophilic Other [24]. (8)) (eq. selenium of presence the in

.Tecneso a nrae o21 to increased was conversion The %.

CfrR=Me, = R for °C

C[6.Aohratcedsrbsteioeiainocrigi ehnlsolutions methanol in occurring isomerization the describes article Another [26]. °C m oen[27]. -oMeBn

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6 23]. [6, % tert btlsbtttdpoutwsol bandin obtained only was product substituted -butyl 2 dut(q 1),abi ihalow a with albeit (12)), (eq. adduct ‘ n pot one Ritch ’ depends (10) (8) (7) (9) 5 Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd ucinlt lorvae eraei obebn hrce on rmSt e F td nrltd2- resonance related 4). on the (Figure study to [33]. DFT contribution form A zwitterionic increased Te. a to an by S to hybrid from trend going this character chalcogenone attributes the double-bond (B3LYP/LAV3P/6-31G(d,p)) for in imidazolones indices bond decrease Wiberg S: a revealed +0.30). is revealed to analysis of +0.0.13 averages also orbital orbital (ca. positive functionality (approximate bond LUMO is Natural charge atom [32]. carbon the negative bound compounds directly partial while these the a of while ring, LUMO bear and imidazole centres HOMO the chalcogen the to the of fragment unit E N = C imidazole C = of the the contributions C and similar revealed Se chalcogenones the benzimidazole HOMO = on and The C (MPW1PW91/LANL2DZ(dp)/6-311G(d,p)) of fragment 6). to ability Section Se respect the (see with = highlight centres antibonding C charge, metal negative to the coordinate partial for to aforementioned character HCUs HOMO the of with and centre along (HOMO) chalcogen these, orbital the and molecular orbitals, occupied p highest centred The are 3. groups Figure aliphatic in more with substituents. substitution those aromatic of more and tel- function with However, telluroureas, a those than is conditions. than slowly solvents soluble soluble and organic ambient more sensitive, more in moisture are under Solubility and selenoureas [32]. light stored typically, solution being pattern; be in as when reported solids can mirrors been have crystalline tellurium and and moisture-stable depositing detelluration chromatography and to column prone air- are generally to luroureas are stable counterparts, are NHC which their unlike selenoureas, Cyclic HCUs of properties General 4 while substrate. acid instance, amino For heterocycles. the six-membered of to substitution isose- the aryl-substituted on strongly or depends alkyl- of reaction the with via lenocyanates accessible are derivatives selenohydantoin Five-membered 6 3: Figure h rnirmlclrobtl fdie(0-X63Gdp) yia C opud r illustrated are compound, HCU typical a (M06-2X/6-31G(d,p)), dmise of orbitals molecular frontier The β Ritch aaieyedda cci iusiue eeorawt orn-lsr rdc observed. product ring-closure no with selenourea disubstituted acyclic an yielded -alanine rnirobtl fdmise. of orbitals Frontier α aioais(q 1) 3] hsmto osntrqiea de ae u conversion but base, added an require not does method This [31]. (13)) (eq. acids -amino N mtyatrnlcai ile ny25 only yielded acid -methylanthranilic – C – nt est ucinlter DT study (DFT) theory functional density A unit. N β Aioaisddntgv ihconversion high give not did acids -Amino − oss rmrl fselenium- of primarily consist 1 − .5 Se: 0.25;

ftedsrdproduct, desired the of % − shows 2 − .0 Te: 0.20; EGRUYTER DE π -bonding − 0.15), (13) (12) (11) π - Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd pcrsoy(e al o uvyo eeatcmons.Terneo hmclsit o h species the for shifts chemical of more ( range be to The expected compounds). telluroureas Those relevant analogues. of survey from a spans for listed 2 Table (see spectroscopy Se( an of gap energy the to [36 correlated the ligands between be NHC to found parent the were of with particular,values properties associated In electronic been [39]. have the phosphinidenes selenoureas of for probes done as been used has been have compounds These 5 5: Figure e. sizes ring atypical HCUs with of found be angles can bond average [35]. NCN this 5) average Figure from The (118°, deviations ring some atoms. large of membered 106(2)°; chalcogen presence be the and to supports carbon This found [34]. the are respectively) between hits, 12 character from bond Å 2.068(12) multiple hits, 88 Structural from Cambridge Å the 5 (1.833(15) in found values ca. distances bond of Te = contractions C and represent Se Database = C average The delocalization. pair lone turing N The features. structural characteristic 4: Figure GRUYTER DE xii eydsaaeceia hfsof shifts chemical disparate very exhibit 2; entry less al 2: Table bonding between correlation any is there if examine to warranted be would the area and this tendencies in study Further 126. to 4 entries in selenoureas δ nr Compound 1 Entry 2 − huhfwri ubr eea ylctluora aebe hrceie by characterized been have telluroureas cyclic several number, in fewer Though several reveal studies These diffraction. X-ray single-crystal by characterized been have HCUs cyclic Many ,ety1 n h mdzln ( imidazoline the and 1) entry 4, π 77 acpigHU nldn mdzl-ae eiaie r on ttelwrfeunyed( end frequency lower the at found are derivatives imidazole-based including HCUs -accepting eand Se Selected δ tutr fa C ihalreNNbn angle. bond NCN large a with HCU an of Structure HCUs. of structure electronic the to contributors Resonance − 5,ety1.Hwvr h eietosaentalcer stesmlrysbtttdTIe n TeIPr and TeIMes substituted similarly the as clear, all not are delineations However, the 1). entry 150, σ bnigeeg a eemndb nrydcmoiinaayi)adceia hf a found. was shift chemical and analysis) decomposition energy by determined (as energy -bonding 125 125 eNRdt o oecci telluroureas. cyclic some for data NMR Te δ eNRsetocpcproperties spectroscopic NMR Te 125 − 6 to 168 eceia hf,a a endn o h eeimdrvtvs[36 derivatives selenium the for done been has as shift, chemical Te – ,wihfaueaklo ezlsbttet,rsnt ntefil arwrange narrow fairly the in resonate substituents, benzyl or alkyl feature which 6, − n em orfetsmlrted shsbe bevdfortheSe-containing been observed has as trends similar reflect to seems and 4 δ − 55 nr )aefuda h ihrfeunyedo h ag,while range, the of end frequency higher the at found are 3) entry 55.5, –

C(=E) n 2 and % δ − π 5 ety1 and 1) (entry 150 acpigaiiyo h aetNClgn.Teceia shift chemical The ligand. NHC parent the of ability -accepting – rmwr spaa,a xetdfrafntoa ru fea- group functional a for expected as planar, is framework N

,rsetvl,cmae otesmo h oaetradius covalent the of sum the to compared respectively, %, π acpig e. -accepting, 77 = R Me: = R H: = R Cl: = R δ eNR( NMR Se ( 125 i e (ppm) Te) Pr: − − − n − − 149.8; 4.08 ) 2(nr ) epciey h benzimidazole The respectively. 3), (entry 52 167.82

→ 168.13 .aclrsbtttdiiaoebsdHCU imidazole-based chlorosubstituted a g. I C=Se) = (C ,7.6 ½, = π

rniin hl ocorrelation no while transition, * )rsnne o aiu cyclic various for resonances %) C Solvent THF-d 125 6 D eNR( NMR Te 6 – 8 38]. I

,7.0 ½, = .aseven- a g. Ritch [73] Reference [13] – δ δ 8,as 38], − − 168, 143

%) 7 Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd dpe ihntersligcodnto oye.Tetn h iadwt hlimI irluaesl in modeis salt Tl diarylaurate by linked thallium(I) coordination metal are a in units abridging engaged with centre ligand thallium(I) (14)) chelated the a (eq. Treating in acetonitrile, yields polymer. motifs THF coordination two resulting exhibit thallium(I)hexafluorophosphate the bis(selenoureas) within with two adopted with reaction complexes Upon thallium(I) elements, [40]. 13 group the Among 13 (groups p-block 6.1 preparation. the in step last multistep the For for number. coordination are and given type are aggregation available) are in solvent (when trends co-crystallized yields of as syntheses, discussion struc- general such crystal a features whose of complexes and favour those in parameters of and omitted structural features block Exhaustive structural by determined. salient categorized on been is focus have section will tures This and HCUs. table, cyclic periodic using the prepared of been group have complexes metal of plethora A chemistry Coordination 6 8 3 4 6 5 Ritch … eadCH and Se – 16) … eitrcin oafr oriainpolymers. coordination afford to interactions Se = R − = R − CH = X Mes, = CH: R = X Dipp, = R – ea odn ihtegl()cnr.Tebimetallic The centre. gold(I) the with bonding metal 129.1 143 i n Pr: Bu: − − 126 130; 2 : − − 55.5 52.4; CDCl CDCl CDCl CDCl 3 3 3 3 EGRUYTER DE [32] [74] [22] [41] Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd -a ifato rNRsetocp,det eylwslblt.Apopou duto aselenourea,via adductof phosphorus A [Mes*N lowsolubility. salt by very phosphadiazonium studied to the be due with to reaction able NMR spectroscopy, not were or but synthesized diffraction were X-ray groups.Fordiiso- complexes tellurourea Analogous aromatic observed. thependent [{LBiX are teractions sizeof type of the complexes bimetallic on groups, depending [LBiX monometallic ofcomplexes, substitution, propylphenyl types different fea- cluster two tetrameric afforded a yielded iodide double bismuth(III) a with derivative turing selenourea hypervalent this of reaction The reported. metal are been tin have selenoureas with complexes complexes two complexes halogen halide The T-shaped hypervalent tin(IV) [41]. of Octahedral (15)) reaction complexes. by (eq. tin prepared several were by HCU benzimidazole represented a are of elements 14 group heavier The GRUYTER DE seco cbn oi e.(6) naohrsuy h s fbliray-usiue selenoureas aryl-substituted bulkier of use the study, another In (16)). (eq. motif -cubane trans 2 oec te ntecodnto pee ograimo lead or germanium No sphere. coordination the in other each to ( μ 3 2 opee eeotie,wiei h aeo mle mesityl smaller of case the in while obtained, were complexes ] -X)} ≡ 2 ]T,hsbe eotd(q 1) [43]. (18)) (eq. reported been has P]OTf, omd(q 1) 4] nbt ae,bismuth cases, both In [42]. (17)) (eq. formed ] Ritch … rlin- aryl (15) (14) (16) 9 Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd hna21rtoo iadtluimi tlzd noeisac R= 10 (R in instance by-product one minor In a utilized. as is obtained ligand:tellurium was of ratio 2:1 a when 60 Te elemental of thebent with bis-adducts are dihalides to ligands afforded selone conversion in acetonitrile benzimidazole slow various a tetrafluoroborate reacting tellurium, aryl- silver T-shaped When HCU-stabilized with cation. of abstraction aryltellurenyl formation Halide HCU-stabilized benzimida- the (19)). of in reaction resulted (eq. The ditelluride halides reported. diaryl tellurenyl been a have HCUs with cyclic dihalides with selenourea elements zole 16 group heavier the of Complexes 10

)cneso opoutwe odce ihecs odrdtluim n h ilsd o improve not do yields the and tellurium, powdered excess with conducted when product to conversion %) Ritch trans oec te ntecodnto niomn ftluim h ecin iemdrt (50 moderate give reactions The tellurium. of environment coordination the in other each to

yield. % IV erhldswsosre e.(0)[1.Tetoselone two The [41]. (20)) (eq. observed was tetrahalides n u r,asur-lnrTe square-planar a Br), = X Bu, EGRUYTER DE II complex (18) (17) (19) – Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd etr recroyi cd u ne h ecincniin hs ucinlgop esterify. groups functional these conditions reaction the under whilethesecond but acid, atzinc, carboxylic free (Se a motif (eq. geometry feature two-coordinate tetrahedral perchlorate with adistorted bent zinc(II) of unusual pre- adducts an structure selenourea been a tetracoordinate is have is both halides known, ofzinc(II)chlo- first zinc(II) are adduct The complexes of [46]. zinc adducts (22)) bis(dmise) other selone Two the simple benzimidazole [45]. was Recently, (21)) [44]. (eq. complex 2002 pared HCU in cyclic reported 12 (21)), group a (eq. of ride structure crystal first The 12 Group 6.2 GRUYTER DE – Zn – ebn nl fc.13) neetnl,teoiia ligands original the Interestingly, 103°). ca. of angle bond Se Ritch (21) (20) (22) 11 Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd e.(5)[8.Oemnmrcmruycmlxwt itre erhda emtyhsbe eotd i a via reported, HgI been with has ligand geometry selenourea/ tetrahedral bidentate distorted a with of complex reaction mercury 1:1 monomeric One [48]. (25)) (eq. oi a loaie rmterato fHgCl of Thedimeric reaction the complexes. two iodidelig- from mercury by bimetallic arisen bridged two also are affords has halides metalcentres motif mercury(II) The with cad- reaction [45]. with analogous (25)) nitrogen The (eq. on afforded ands. substituents was complex alkyl bimetallic -containing a with iodide, ligand mium selonourea benzimidazole a reacting By one ligands, selenourea two 2,6-diisopropylphenyl featuring of form. complex to case neutral observed the is a In chloride, centres, (LCdCl one cadmium. nitrogen form and at the the of geometry on polymer bipyramidal substituents coordination reaction trigonal (Dipp) sub- a the distorted aryl used, in with obtained is the is nitrate When obtained, ligands cadmium [46]. selenourea is when (24)) three and and (eq. perchlorate chloride HCl one cadmium methanolic structural with with unique complex in three cationic salts (22)), a cadmium eq. Mes, in are with (as stituents reacted ligands when aryl/alkyl obtainable mixed are Using [47]. motifs (23)) (eq. 2007 hexafluorophosphate in cadmium(II) reported was of adduct dmise A 12 Ritch 2 ihadctoi ieeie i laaeo h Se the of cleavage via diselenide, dicationic a with – h is ooetcselenourea homoleptic first the 2 e.(26)). (eq. – amu complex, cadmium EGRUYTER DE – ebond Se (23) (25) (24) 2 ) x Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd ms ihcpe(I rfae(q 3) 5] nti ecin noiainpoutoftheHCU,[(dmise) product oxidation of an 15 coordination in thisreaction, reductive In isolated the also by [52]. was afforded (31)) is (eq. small the where complex triflate cationic copper(II) homoleptic adducts with the A dmise planar rings. trigonal imidazole affords feature the (30)) between (eq. tions Cu halides a copper(I) is with either of are dmise exception ligands of two An complexes with reaction analogue. 2:1 selone The benzimidazole bis(selone) number [45]. a bridged (29)) of methylene nuclearity/coordination complex the iodide copper(I) higher or dimeric ligand the (dmise) selone of dimethylimidazole all Nearly complexes The chalcogenone. the Cu of Se contain 180° some used by featuring salts state, metal metal solid the The the of [49]. in reduction (27)) centrosymmetric with (eq. are concomitant centres is nitrogen complexation the the the ligandalong on so of installed characterized groups structurally aryl properties bulky all Cu andelectronic with two-coordinate of Cationic the half steric counterion. on one the over with depending significantly, up vary make complexes metals copper the coinage of complexes HCU writing, cyclic of time the At 11 Group 6.3 GRUYTER DE naohrrpr,anurltocodnto oprI ope a bandb h ecino eybulky very a of reaction ClO [50]. the = (28)) by (eq. X obtained toluene was Mes, in complex = CuBr copper(I) with (Ar two-coordination selenourea pseudo-centrosymmetric neutral a is report, and another group In space another in crystallized – ea dut,ado hs h aoiyaeo opr h ulaiyadcodnto ubrof number coordination and nuclearity The copper. of are majority the these of and adducts, metal syn

yield. % X=B,I or I) Br, = (X anti X=C)[1.The [51]. Cl) = (X I opee aebe bandb sn eeoraligands selenourea using by obtained been have complexes – Cu syn – ebn nls xetfroedrvtv,which derivative, one for except angles, bond Se ofre xiisintramolecular exhibits conformer n btlgop ntentoe ete (eq. centres nitrogen the on groups -butyl 4 7°bn angle). bond 176° ; π – Ritch π 3 ][OTf] interac- II N,N and , (27) (26) (29) (28) 13 2 ′ - , Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd etrn w oprcnrs ahceae yoebieadbigdtgte yatidlgn e.(4) The (34)). (eq. ligand third a by together bridged and bmise one complex Cu by a 3:2 ligand:metal central chelated The each [55]. centres, afforded characterized copper tetrafluoroborate two structurally tetrakis(acetonitrile)copper(I) featuring and with bmise synthesized of been reaction have 1:1 copper(I) featuring complexes dinuclear Four sites. equatorial geometry, the bipyramidal of trigonal one distorted in a atom exhibits donor centre selenium copper(II) The the the [54]. with Cu in (33)) state bind (eq. oxidation to dmise +2 was struc- the with One ligand stabilize ordination [53]. to selenourea (32)) used reducing strategy (eq. the The ligand reported. of tridentate been presence the has by also centre followed copper(II) dmise, are a with containing ligands salt ture tris(pyrazolyl)borate-type copper(I) a and of tris(pyrazolyl)methane reaction by and accessible dmise of complexes Heteroleptic 14 Ritch 2 Se 2 igi butterfly-shaped. is ring II with π aii hnnhoielgnspirt co- to prior ligands phenanthroline -acidic EGRUYTER DE (31) (30) (33) (32) Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd nrcn er,adteemtl aeteptnilt qa h tutrldvriyo opr ev group Heavy copper. of diversity structural the equal to potential the characterized have structurally metals been have these complexes and of years, number a recent However, explored. in thoroughly less much (16), is centres ligands. gold eq. copper(I) selenourea in and The complex halide positions. tetrabismuth both bridging by the in bridged with from ligands are iodide distinct halide and or quite tetrahedral only bromide are is with copper(I) structure coordination of The octahedral reaction [51]. featured 1:1 which (37)) simple (eq. the acetonitrile by in prepared dmise, was complex tetrametallic neutral A exhibiting of centres sphere copper coordination both with the cen- (36)). complex, completes selenium (eq. bimetallic ligand Theother geometry another dmise afforded planar terminal dmise trigonal ligand. one only Cu bmise and Using central different centre. terminal, the a metal is each to case ligand belonging bidentate this donor each (35)), in on selenium (eq. but tre fashion bridging formed, stepwise each is a with coordination in planar, tetrahedral ligands is chalcogenourea with bidentate complex and bimetallic monodentate another of mixture a using When GRUYTER DE oprdt opr h ylcHUcodnto hmsr ftehairgop1 lmnssle and silver elements 11 group heavier the of chemistry coordination HCU cyclic the copper, to Compared Ritch 2 Se 2 ring (35) (34) (37) (36) 15 Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd Ag 6: Figure coordinate four are sites silver the of Two Ag weak 2:3. the to including 1:1 coordinate, from In three altered 6). is been (Figure one has environments and silver(I) ratio distinct ligand:metal crystallographically the NO three product, = with this X polymer Mes, coordination = a (Ar of complex mation silver bimetallic one of Recrystallization complexes. bimetallic yielded group Mes encumbered sterically less the the from [57]. arise more [36 for analogues to observed mesityl-substituted surmised were smaller was complexes the gold ionic for of seen mode observed were aggregation cationic neutralbimetallic were centres The used, but and complexes metal adducts was ionic three-coordinate ligand chloride silver, with aDipp-substituted selenourea-gold(I) For complexes when neutral [56]. anions) or dinitritoargentate seen: counterion aryl- were dichloroaurate triflate using (featuring types fashion, a structure equivalent theelements. with two an all complexes in gold, bis(selenourea) between prepared of differences be noteworthy case however, can are, the (27) There In eq. (38)). in (eq. complexes selenoureas copper cyclic substituted linear the of analogues 11 16 [21]. (39)) (eq. ligands bmise 4 – h ecino rpeypopiesle()tilt n ms foddattaealccutrfauigan cluster featuring atetrametallic afforded bmise and triflate silver(I) triphenylphosphine of reaction The Se 8.I h aeo ivr h uke ipgop emdt rmt h ooealcincfr,while form, ionic monometallic the promote to seemed groups Dipp bulkier the silver, of case the In 38]. 6 Ritch imnodcr,wt h orsle ete apdb emnlPPh terminal by capped centres silver four the with core, diamondoid ivrI oriainplmrfauigHUligands. HCU featuring polymer coordination silver(I) A π acpigslnues(sjde ythe by judged (as selenoureas -accepting … otc hc ik h ooestogether. monomers the links which contact O π acpigntr fteslnue ligands: selenourea the of nature -accepting 3 rmhtmtao eutdi h for- the in resulted methanol hot from ) 3 iad n obybridging doubly and ligands 77 eceia hf value) shift chemical Se EGRUYTER DE (38) Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd ntepoutcmlxidct omto fplaimslnd hssa ieysd reaction. side likely a selenium atom as missing phases selenide and palladium yield of low formation The indicate complex product. product the monodechalcogenated in aneutral, a dicationic afforded complex afforded dium the PdSe conditions precursor, square-planar, ligand exchange a pincer SeCSe anion with potential complex under a rep- from also bis(benzonitrile)dichloropalladium(II) Starting is complex. with Palladium(II) neutral [61]. reaction one (44)) and (eq. cationic ligand one macrocyclic by a resented featuring adduct selenourea octahedral NiBr distorted neutral one reported: been have plexes M of lack M Several 10 Group 6.4 centres. metal c.f. proximity, square-planar close exhibits into complex brought gold(III) than the rather while (42)), 34 (eq. Equations ligand in a whole complexes the copper(I) saltsin by the bridged of intwobimetallic are ligands centres selone) Treatment bis(imidazole metal salts resulted mixed-valent of the a use which and gold(III) The characterized. yielded [59]. gold(I) ligand (40)) pentafluorophenyl-substituted (eq. selenourea with been anion combination multidentate gold(I)-containing in a a and have with cation gold(III) acid a complexes tetrachloroauric with salt HNEt of coordination and reaction The selenourea [58]. diaryl gold(III) (40)) a with and complex hydroxide gold(I) (NHC)gold(I) more Several GRUYTER DE IV II opee st eepce,gvnterdcn aueo h hloeora.Tonce(I com- nickel(II) Two chalcogenoureas. the of nature reducing the given expected, be to is complexes (d 8 opee fcci Cshv ensnhszdadcaatrzdb -a ifato.The diffraction. X-ray by characterized and synthesized been have HCUs cyclic of complexes ) 4 oe(q 4) 2] h aebsslnue)i ecinwt dipalla- a with reaction in bis(selenourea) same The [22]. (45)) (eq. core – 5[1.A xetd h odI ope etrslna coordination, linear features complex gold(I) the expected, As [21]. 35 2 dutwt erhda emty(q 4) 6]adoecationic, one and [60] (43)) (eq. geometry tetrahedral with adduct 3 foddahtrlpi ope (eq. complex aheteroleptic afforded F Ritch (41) (40) (39) (42) 17 Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd iei ope eeotie yrato ihaay-rde i(eeora iad(q 4) 6] When [63]. (47)) (eq. C aryl ligand the bis(selenourea) across aryl-bridged addition palladium idative one a and Pd with platinum the reaction One with other. by reacted each obtained towards were oriented ligand complex each dimeric of substituents methyl smaller the two the being with centre motif, metal butterfly-shaped palladium(II) a rather bridging featuring but complex experiment square bimetallic growth a crystal yielded in A chloride atoms known. palladium(II) selenium also and are selenourea platinum, imidazole of an one featuring and palladium, of complexes dinuclear Several 18 Ritch cis 0 orePd source rettos(q 4) 6] nietesle opee ne.(8,tecnrlrn snot is ring central the (38), eq. in complexes silver the Unlike [62]. (46)) (eq. orientations 2 (dba) syn – rbond. Br oec te.Teiiaoernsaeas eryi h aepae with plane, same the in nearly also are rings imidazole The other. each to 3 h aelgn ile nitatbemxuewt odtcal ox- detectable no with mixture intractable an yielded ligand same the , cis hoielgnscmltn ahsquare-planar each completing ligands chloride EGRUYTER DE (45) (44) (43) (46) Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd iett iadwt n ezmdzl eeoradnradete edn ho rslnehrsub- selenoether or thio- pendant [66]. a (51)) (eq. either a atoms and featured nitrogen donor complex the of selenourea rhodium Ir one benzimidazole The related on Two one stituent [65]. chloride. with was (50)) ligand counterion (eq. the bidentate iridium centre a for metal while the anion, complex chelating [Cp*MCl [Cp*MCl] rhodate(III) ligands the dimeric to the the adducts featuring with as complexes represented ligands all bis(selenourea) are Mixing elements 9 ment. group heavier the of Complexes mixture racemic a reveals packing the chains. CoCl and helical cobalt, with right-handed ligand at and coordination the left- tetrahedral of of features reaction structure upon The obtained to was [60]. bis(selenourea) (49)) similar a adduct of polymer bis(selenourea) coordination monomeric A A characterized. structurally ZnCl been have complexes cobalt Two 9 Group 6.5 GRUYTER DE 2 (dmise) 2 e.(1)wspeae ybiigdw ehnlco h iadadmtlsl e.(8)[64]. (48)) (eq. salt metal and ligand the of methanolic a down boiling by prepared was (21)) (eq. 2 ] 2 opee foddctoi monomeric cationic afforded complexes III + opee feature complexes M=R,I)frag- Ir) Rh, = (M 2 nTF(eq. THF in Ritch (47) (49) (48) 19 Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd h n n nycytlsrcueo ru ope facci C ae akt h 90rpr fthe of report 1980 the to back withaCr dates HCU cyclic tellurourea a of the imidazoline of complex 6 Treatment group [16]. a tellurourea of well-characterized structure first crystal only and one The 6 Group 6.7 same the using generated [68]. are reaction. (53) complexes complex hydrolysis eq. ruthenium(II) acationic in cationic its Two shown yields (31). via tetrafluoroborate eq. procedure scavenger iron(II) in water with complex dmise copper(I) a of the and reaction to 4:1 solvent similar the a that both discloses report as same The acts (dmise) orthoformate CH adduct triethyl in simple the tetrahydrate The conditions, chloride reported. iron(II) are and ligand salts the iron(II) of adducts dmise Two 8 Group 6.6 20 Ritch 2 Cl 2 /HC(OEt) 3 ovn ytm(q 5) 6] ne these Under [67]. (52)) (eq. system solvent 2 FeCl 2 a rprdb mixing by prepared was 0 oreafforded source EGRUYTER DE (51) (50) (53) (52) Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd Dipp Dipp Dipp* Dipp* Mes DBU Abbreviations written. was chapter the this to of visit portion sabbatical a JSR’s which hosting University during for the 2017, thanked summer and is in (Canada) Burford Victoria Neil Council of Prof. University Research acknowledged. Engineering gratefully and is Winnipeg Sciences Natural of the from support Financial reactivity. of Funding modes and types structure new pace, more even this Given of complexes. discovery metal the resultant for their promising and very ligands looks these future of the chemistry structural and synthetic the of chalcogenide metal new other generate to potential the has chemistry of clusters. met- type Mn This chalcophilic (MnTe) [69]. a to fragment which NHC with tellurium in maining tellone transfer products 1,3-diisopropylimidazole may insertion of which yield ligands, reaction may to bond non-innocent the Te new = instance, ad- C of For the be design als. of could stability the issues chemical in lower solubility Tellurourea The exploitable nitrogen. available. be on complexes substituents metal lipophilic stable installing by of dressable range the increase to multifunctional carbenes, using by expanded greatly (e. be ligands could telluroureas hybrid and seleno- both of of solubility chemistry coordination lower the the given stability. understandable, chemical lower is their data chem- and of selenoureas, coordination paucity to of This compared studies example. telluroureas crystallographic reported time in single the represented only at barely absent with known. are completely istry, derivatives not are softer tellurium complexes are complexes for metal The f-block HCU writing. preference and and which of a s-block for cores of shows metals heterocyclic studies clearly many crystallographic different remain particular, HCUs There In with of metals. designed chemistry d-block build- be late coordination routes, particularly can The synthetic metals, They reliable nitrogen. NHCs. of on of number substituents a chemistry organic by well-explored accessible the are upon tellurium ing and selenium featuring HCUs Cyclic outlook and Conclusions 7 20 at decomposes slowly It Cr(CO) complex. the tellurourea to ligand of adduct 1:1 the GRUYTER DE vrl,teceityo ylcHU ean eyatv,wt ayrcn tde lbrtn e aspects new elaborating studies recent many with active, very remains HCUs cyclic of chemistry the Overall, possible is It compounds. these of explorations future for opportunity exciting an represents this However, OMe ,,-rmtypey (mesityl) 2,4,6-trimethylphenyl OMe 1,8-diazabicyclo[5.4.0]undec-7-ene 2,6-diisopropylphenyl 2,6-bis(diphenylmethyl)-4-methylphenyl 2,6-diisopropyl-4-methoxyphenyl 2,6-bis(diphenylmethyl)-4-methoxyphenyl

.ceaigbdnaeo rdnaelgns etrn togdnr uha hshnsor phosphines as such donors strong featuring ligands) tridentate or bidentate chelating g. 5 rget(q 5).Ti sas h nysrcual hrceie cyclic characterized structurally only the also is This (54)). (eq. fragment n lsesfre uaeaddcbn ois iae ytere- the by ligated motifs, dicubane and cubane formed clusters

Ci oun ouinvadetelluration. via solution toluene in °C 0 rcro a eetyshown recently was precursor Ritch (54) 21 Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd OTf THF IMes IPr dmise NHC MW HCU dba Bmise Bn 2]GaaeN ajr T ig B uce J i(hloeoe)a icrlgns slto n ekatvt fteselone-ligated the of activity heck and isolation ligands: pincer as Bis(chalcogenones) RJ. Butcher HB, Inorg Singh ST, J Manjare Eur N, derivatives. Ghavale selone [22] or imidazoline-2-thione with complexes 11 Group V. Lippolis A, Laguna M, Kulcsar MC, Gimeno MT, Aroz [21] by nitration proteintyrosine peroxidase-mediated and peroxynitrite- of Inhibition G. Mugesh S, Jayavelu K, KP, Satheeshkumar Bhabak [20] di- with derivatives imidazole-2-selone of Reaction al. et ML, Mercuri V, Lippolis FA, P, Devillanova Deplano MA, Pellinghelli F, Bigoli differ- [19] reactivity the and tetrahydrofuran in diselenides and selenides metal alkali of synthesis convenient P. A DP, Boudjouk Thompson Com- [18] Chem Soc Chem J (C5H8N2S). 1,3-dimethyl-2(3H)-imidazolethione of structure molecular The DW. Moore DM, Forkey GB, of Ansell structure [17] molecular and crystal The complexes: metal transition derived and Telluroureas GM. McLaughlin TR, Martin MF, Lappert [16] 1,1 aus 1,3-diphenyl-2-imidazolidinselenon II. reaktivität, extremer mit C=C-doppelbindungen W. Stephan E, Singer 1993;48:973 B. A, Naturforschung Schönberg Für [15] Z 2-selenoimidazoline/2-selenoimidazolines. T. Kratz carbene G, mixed Henkel and N, Kuhn carbene [14] stable air An al. et WJ, Marshall D, Khasnis JR, Goerlich HV, Dias F, Davidson AJ, Arduengo [13] 2-telluroimidazoline III. Imidazols, des chemie zur Beiträge T. Kratz 1993;561 G, Synthesis. Henkel imidazole-2(3H)-thiones. N, of Kuhn reduction [12] by 1991;113:361 Soc. imidazol-2-ylidenes of Chem Synthesis Am T. J Kratz carbene. N, crystalline Kuhn stable [11] A M. Kline RL, Harlow AJ, Arduengo Rev. [10] Chem precursors. carbene N-heterocyclic to routes Synthetic V. César S, Bellemin-Laponnaz G, Lavigne E, Chardon 2005;237 L, Chem. Benhamou Org [9] J 2005;249:829 Rev. Eur nonmetals. Chem of Coord chemistry. complexes element Carbene W. group Kirmse main [8] their and 3-dihydroimidazol-2-ylidenes 2, A. Al-Sheikh N, Kuhn mechanistic [7] A selones: and thiones imidazole-based by oxidation lactoperoxidase-catalyzed 2014;28:61 of Chem. Inhibition Organomet Appl G. selenoureas. Mugesh PN, of Jayaram applications G, biological Roy and [6] Synthesis A. Shah A, Badshah RA, Hussain [5] chemistry, coordination metal transition row first late their compounds, selone-containing and Thione- JL. Brumaghim BS, Stadelman [4] K.I., Priyadarsini V.K., Jain In: applications. biological potential with donors imidazoline-2-selone of chemistry relevant The V. PbSe Lippolis to [3] precursors selenourea of library A al. et GT, Cleveland RA, Swain W, Walravens AN, MP, Beecher MP, Hendricks Campos [2] precursors. nanocrystal chalcogenide cadmium of reactions Conversion JS. Owen H, Liu BM, MP, Cossairt Hendricks R, García-Rodríguez [1] References 22 sele- and with orthoformate triethyl of Reaction 13: Part compounds. subvalent of reactivity and Synthesis MK. Denk Y, Zhou [23] benzyl nymtia C,C,Se unsymmetrical 2011;2884 Chem. 2011;9:7343 Chem. Biomol Org derivatives. selenourea and thiourea imidazole-based 1993;124:445 Ital. Chim Gazzetta selenanide bis(dichloromethane). diiodo selenanide)ethane 1,3-dimethyl-4-imidazolin-2-ylium diiodo compounds: 1,2-bis(3-methyl-4-imidazolin-2-ylium selenium and hypervalent I-Se-I of examples first the of and 1,1￿-bis(3-methyl-4-imidazoline-2-selone)methane bis(diiodine) adduct the of characterization spectroscopic and structural Synthesis, iodine: 1988;53:2109 Chem. Org J ultrasound. of Effect bromides. organic toward salts these by exhibited ences 56b 1970 mun 1980;635 Commun. Chem Soc Chem J [Cr(CO)5{TeCN(Et)CH2CH2NEt}]. tetraphenyl- 1997;119:12742 Soc. Chem 1993;126:2047 Ber. 2011;111:2705 Chem study. sele- sulfur, 2013:33 Society, of Chemical chemistry American biological USA: The DC, chemistry: Washington, tellurium. Biochalcogen editor(s). and J.L., nium, Brumaghim C.A., Bayse In: potential. biological their and 2017:122 Chemistry, of Society Royal UK: London, medicine. and biology in compounds Organoselenium editor(s). 2017;139:2296 Soc. Chem Am J limit. homogeneous the near distributions size with nanocrystals 2013;25:1233 Mater. Chem nium N,N dibenzylideneacetone rfurmtaeufnt (triflate) trifluoromethanesulfonate microwave tetrahydrofuran N,N ev chalcogenourea heavy N Ritch N,N bis( — ′ htrcci carbene -heterocyclic -bis(2,6-diisopropylphenyl)imidazol-2-ylidene ′ ovnetoese he-opnn ytei o eeora.TtaernLt.2003;44:1295 Lett. Tetrahedron selenoureas. for synthesis three-component one-step convenient A -bis(2,4,6-trimethylphenyl)imidazol-2-ylidene N ′ dmtyiiaoeselone -dimethylimidazole mtyiiaoeselone)methane -methylimidazole Δ – – – 2,2 33. sa .2013;8:1910 J. Asian 7. – ′ biiaoii n ee.Ce e.1983;116:2068 Ber. Chem selen. und -biimidazolidin – 94. 9. – dpne ope.Dlo rn.2015;44:11893 Trans. Dalton complex. pincer Pd – – 9. 49. – 21. – – – – 73. 60. 900. 7. – 70. – 50. — tbl elrcroy-ebnugn Chem tellurocarbonyl-verbindungen. Stabile – 3. – 305. – 12. – – 9. 7. – 2. – 49. “ ies.JAm J dimers”. – 73. EGRUYTER DE – – 54. 57. ′ ,3,3 ′ - Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd 5]BaeA,Lpoi ,PvtaT eaiG (1,3-Dimethyl G. imidazolidine-2-selone- Verani T, Pivetta V, Lippolis AJ, Blake Cu(I)-chalcogenone[54] using sulfur and selenium of action antioxidant the Probing D. VanDerveer JL, Brumaghim MM, Kimani biologi- [53] of kinetics reduction Cu(II) and electrochemistry, coordination, copper the Investigating JL. Brumaghim HC, variable Wang with MM, complexes Kimani Cu(I) [52] selone and thione of studies DFT and characterization, Synthesis, JL. Brumaghim CA, Chem. Bayse Inorg MM, complexes. Kimani chalcogenone [51] silylene copper(I) to approach Unique HW. Roesky SK, Pati S, Das S, Khan S, Pal Dal- N, . Parvin unsymmetrical [50] of borylation in application and synthesis chalcogenones: Cu(I) Linear G. Prabusankar CN, adsor- Babu mode K, Dual Srinivas imidazoline-2-selenone: [49] bearing particles Submicro-polymer al. et JH, Nam K, Ihm HJ, Kim HY, Yang SY, Park J, Choi [48] of analysis structural X-ray and characterization preparation, The D. KP, VanDerveer Gwaltney B, aqueous Baker in BJ, McKinney reactions DJ, barbier Williams for catalysts [47] active Highly selones: cadmium and zinc to access Facile G. Prabusankar K, d10-metal Srinivas and CN, d8- Babu with [46] selones of Complexation dihaloselones: and selones of reactivity and Synthesis RJ. Butcher HB, Singh S, Yadav [45] selenide zinc potential A AP. Dichlorobis[1,3-dimethyl-2(3H)-imidazoleselone]zinc(II): Wilkinson D, VanDerveer KM, White DJ, Lewis Williams phosphadiazonium [44] a on ligands Chalcogeno-urea R. McDonald TS, Cameron KN, Robertson HA, Spinney AD, Phillips N, Burford [43] Potential bismuth(III)trihalides: of complexes chalcogenone Heavier G. Prabusankar A, Sathyanarayana CN, P, Babu Suresh K, Srinivas [42] N-heterocyclic-carbene- and Bi) Sn, (Te, elements main-group between reaction Redox RJ. Butcher HB, Singh AuI S, heteropolynuclear Yadav ST, and Manjare TlI [41] Homopolynuclear al. et T, Lasanta A, Laguna M, Kulcsar M, Gimeno Concepción T, Aroz M, Arca [40] 31P G. Bertrand D, Martin CD, Martin J M, Henry-Ellinger Eur O, parameters. Back NMR [39] 77Se from carbenes N-heterocyclic of properties ligand the Determining C. Ganter W, Frank H, Buhl K, Verlinden [38] the Determining C. Ganter K, Schaper H, Buhl and K, Verlinden selenoureas A, of Liske spectroscopy [37] NMR can What al. et AMZ, Slawin DB, Cordes A, Gómez-Suárez A, Poater DJ, Nelson SV, Vummaleti [36] hexahydrobis[(1,3-p-dimethylaminobenzyl)-1,3- of structure crystal and 2008;2832 Synthesis Trans. B. Dalton Çetinkaya revisited. E, radii Kendi Y, Covalent Gök al. E, et Çetinkaya E, M, Cremades Aygun J, [35] Echeverría M, Réves AE, Platero-Prats V, Gómez B, Cordero counter- [34] chalcogen heavier their with Comparison 2-imidazolones: of characterization Structural G. Parkin B, Kriegel A, Al-Harbi Y, Rong [33] carbon the of Nature benzimidazolin-2-chalcogenones: of synthesis Facile RJ. Butcher HB, Singh S, Sharma ST, Manjare and [32] isoselenocyanates from selenohydantoins of Synthesis T. Watanabe M, Honda M, Takashima K, Sakata H, Maeda M, Segi [31] selenothiocarboxy- and diselenocarboxylate stable Isolable, A. 1969;34:3549 Ishii Chem. A, Org Sakamoto Y, J Sugihara thioureas. T, from Kitahara J, Nakayama selenothiocarbamic [30] and selenoureas of Synthesis RJ. Shine DL, Klayman [29] proper- the of study the to approach theoretical and experimental An al. et V, Lippolis F, Lelj F, Isaia FA, Devillanova F, Demartin M, Arca [28] nitration tyrosine protein peroxynitrite-mediated against protect analogues their and drugs Antithyroid G. drugs. KP, anti-hyperthyroid Mugesh by Bhabak biosynthesis [27] hormone thyroid of inhibition the of aspects chemistry Bioinorganic G. Mugesh D, Ed. Das Int G, Roy Chem [26] Angew organomercurials. of detoxification Chemical G. Roy B, Pathak K, Muthuvel KS, Rawat R, Karri M, Banerjee crystallographic [25] X-ray and characterization, Synthesis, al. et RL, Jones YT, Pang D, VanDerveer RR, Raye MR, Fawcett-Brown DJ, Williams [24] GRUYTER DE 5]Kmn M at ,Gaa A aioihD a P rmgi L iula oprI opee ihNhtrcci hoeand thione N-heterocyclic with complexes copper(I) Dinuclear JL. GP, Brumaghim Yap D, Rabinovich LA, Graham D, Watts MM, Kimani [55] 2007;63:m364 bis bis (2,2 and (perchlorate) 2010;49:9200 Chem. Inorg complexes. -borate and tris(pyrazolyl)methane 2012;41:5248 Trans. Dalton compounds. thione and selone relevant cally 2011;40:3711 Trans. Dalton geometries. coordination 2017;56:1706 2015;44:15636 Trans. ton 2011;2:2512 Chem. Polym ions. mercury and halogens for color-sensing with bents 2007;37:691 Crystallogr. Chem J hexafluorophosphate. tetrakis[1,3-dimethyl-2(3H)-imidazoleselone]cadmium(II) 2016;45:6456 Trans. Dalton media. 2017;2968 Chem. Inorg J Eur ions. 2002;5:124 Commun. Chem Inorg synthon. Ch to approach synthetic new A acceptor: 2015;5:15579 Adv. RSC . cyclic of cleavage acylative for 2013;5344 catalysts Chem. Inorg J Eur halides. monomeric of preparation the for method facile A halides: selenium derived 2011;2288 Chem. Inorg J Eur interactions. intermetallic by luminescence of Activation ligands: organodiselone with plexes the of 2015;2416 Chem. Inorg 2013;32:5269 Organometallics. adducts. selenium their of shifts chemical NMR 77Se the about us teach phosphinidenes 2003;19:1093 Sci. Anal C23H32N4Se. diazepine]-2-selenone, 2013;52:7172 Chem. Inorg parts. 2012;717:61 Chem. Organomet J bond. 2010;82:1709 Heterocycles. acids. 2000;122:9120 Soc. Chem Am 2-(1,3- J dimethylimidazolidinio)selenothiocarboxylate. and 2-(1,3-dimethylimidazolidinio)diselenocarboxylate of reactivities and structures, Syntheses, salts: late Chem. J Can diethylimidazolidine-2-selone-4,5-dione. of structure crystal and 2000;78:1147 Synthesis compounds: related and acid parabanic of ties Chem study. mechanistic 2007;360:303 Acta. Chim Inorganica 2015;54:9323 1993;4:409 Chem. Heteroat 1,3-dimethyl-2(3H)-imidazoleselone. of structure eoelgns ytei,caatrzto,adeetohmclsuis atnTas 2015;44:16313 Trans. Dalton studies. electrochemical and characterization, synthesis, ligands: selone π acpigpoete fcree.AgwCe n d 2016;52:2939 Ed. Int Chem Angew carbenes. of properties -accepting – – – 12. 7. – 57. 7. – 25. – 44. – u .2010;16:1175 J. Eur ′ -bipyridyl- – 82. – – – 17. 79. π 65. – acpigaiiiso -eeoylccree? hmSi 2015;6:1895 Sci. Chem carbenes?. N-heterocyclic of abilities -accepting 16. – κ 74. 2N,N − – od C ,S e.IogCe.2003;42:4949 Chem. Inorg Se). S, O, = (Ch bonds P 6. – ′ )(imidazolidine-2-thione- 85. – 23. – 4.

M hmclsit fcarbene of shifts chemical NMR π acpo rpriso -eeoylccree ymauigthe measuring by carbenes N-heterocyclic of properties -acceptor – 90. – κ 59. )oprI)bs(eclrt) caCytlorC. Crystallogr bis Acta S)copper(II) (perchlorate). – 11. – – κ 43. 14. Se)bis (1,10-phenanthroline- – 6. – 7. – 72. – 54. – hshndn dut sa indicator an as adducts phosphinidene – 24. κ – 2N,N 904. – ′ – )copper(II) 4. 57. – chalcogen – – 51. 97. Ritch α – -amino l com- TlI — – 8. A 23 Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd 7]LuL h ,CoL,SehnD.Nhtrcci abn tblzdprn ufnl eeey,adtluey ain X+ ,S,Te). Se, S, = X (XH+, cations tellurenyl and selenenyl, sulfenyl, parent stabilized carbene N-heterocyclic DW. Stephan LL, Cao D, Zhu L, in Liu liganden [74] Als 2-chalkogenoimidazoline Xxii. liganden Als Heterocyclen G. Henkel M, Steimann T, Kratz R, Fawzi N, Kuhn imidazole-2- [73] yield to acetates imidazolium with chalcogens elemental of Reaction RD. Rogers JD, Holbrey G, Gurau H, Rodríguez [72] Carbon al. et B, Mallick F, Kniep L, Gomes M, Düser Ru-N-heterocyclic L, of P, Vogel selectivity Wonner the [71] understanding and Exploiting al. et C, Copéret A, Fedorov W-C, CP, Liao Gordon CB, Chem. Santiago Inorg PS, nuclearity. Engl core [70] cluster molecular telluride manganese of control Ligand X. Roy ML, Steigerwald hydro- T, transfer Siegrist DW, of Paley activation B, catalytic Choi in [69] source hydrogen as glycerol vs 2-Propanol AK. Singh PL, Gupta KN, Sharma H, Joshi AK, Sharma [68] electrochemical and calculations, DFT characterization, Synthesis, JL. Brumaghim CD, McMillen CA, Bayse MM, Kimani BS, Stadelman [67] ( of Complexes AK. Singh R, Bhaskar H, Joshi AK, Sharma [66] with complexes rhodium(III) and iridium(III) half-sandwich of structures and Syntheses G-X. Jin Y-J, Lin Y-B, Huang W-G, Jia [65] Dichlorobis[1,3-dimethylimidazole-2(3H)selone-Se]cobalt(II). al. et WT, Pennington JA, Ritchie KJ, Davis ED, Rice TA, Jones J DJ, Eur Williams studies. [64] structural and Synthesis gold(III): and platinum(II), palladium(II), of complexes Bis(selone) RJ. Butcher HB, Singh mech- V, and Rani liquids [63] ionic hydrophobic with extraction palladium(II) towards behavior Selone Y. Yang H, Zhang Y, Huang Y, Tong C, Wang [62] aza Mixed al. et F, Isaia A, Garau L, Esriche FA, Devillanova J, Casabò ligands AJ, Se) Blake (S, [61] organochalcogen with polymers coordination cobalt and complexes Nickel G-X. Jin G-L, Wang Y-J, Lin Y-B, Huang lig- W-G, selone Jia pyridine-based [60] with complexes gold of activity catalytic and characterization Synthesis, C-C. Ji Q-T, Chem- Xu bifluorides. W-G, gold Jia H-N, by Zhang catalysed [59] alkynes of Hydrofluorination al. et DB, Cordes A, Obled M, Brill D, Bello SR, Patrick F, Trans. Nahra Dalton [58] ligands. selenourea cyclic with chemistry coordination silver(I) Diverse JS. Ritch MA, Wiebe SM, Mezibroski gold(I). JH, to Perras selenoureas [57] cyclic of coordination the SP. Exploring Nolan AM, Slawin DB, Cordes SR, Patrick F, Nahra DJ, Nelson [56] 24 atnTas 2017;46:3095 Trans. Dalton 1996;108:107 Elem. Relat Silicon Sulfur Phosphorus pentacarbonylmetall-komplexen. 2011;47:3222 Commun. Chem proto-carbenes. as liquids ionic for evidence direct chalcogenones: 2017;56:12009 Ed. Int Chem Angew to olefins cyclic of ethenolysis the for catalysts metathesis carbene 2015;54:8348 ( with genation 2016;45:4697 Trans. Dalton ligands. selone and thione with complexes iron(II) novel of comparison Trans. 2017;46:2228 Dalton synthesis. benzimidazole 1,2-substituted and oxidation for Catalyst dihydrobenzoimidazole-2-thione/selenone: Trans. Dalton polymerization. norbornene for catalysts as 2008;5612 use their and N-methylimidazole bearing ligands Se) (S, organochalcogen 1997;53:837 C. Crystallogr Acta 2017;3720 Chem. Inorg 2015;5:63087 Adv. RSC studies. anism 1999;1085 Trans. Dalton Soc Chem 92. J 2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane}. = {L [NiL(MeCN)][BF4]2 in reactions Substitution 2008;4063 Chem. Inorg J Eur properties. and structures, Syntheses, moiety: N-methylimidazole an bearing 2016;450:315 Acta. Chim Inorg ands. 2015;7:240 CatChem. 2018;47:1471 2014;33:3640 Organometallics. Ritch – 20. – – – 8. 55. 37. η -ezn)uhnu(I opee fusmerclbdnaecacgnlgns raoealc.2014;33:3629 Organometallics. ligands. chalcogen bidentate unsymmetrical of complexes 6-)ruthenium(II) – 4. – 8. – 9. – – 8. 5. – – 12. – 20. 94. η -p)rII ih1-benzyl-3-phenylthio/selenomethyl-1,3- with 5-Cp*)Ir(III) α , ω – aoe odatvto yslnu-ae hloe bonding. chalcogen selenium-based by activation bond halogen dee.JA hmSc 2017;139:13117 Soc. Chem Am J -dienes. – hacon otiigte11-hnnhoiesub-unit. 1,10-phenanthroline the containing crowns thia – 19. – 4. – 711. – 73. – 25. EGRUYTER DE – – 39.