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[Ph4c4si(Me/Cl)-(Me/Cl)Sic4ph4] from Silole Anion [Mesic4ph4]

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[Ph4c4si(Me/Cl)-(Me/Cl)Sic4ph4] from Silole Anion [Mesic4ph4] molecules Communication 0 Synthesis of 1,1 -Bis(1-Methyl/Chloro-2,3,4,5- Tetraphenyl-1-Silacyclopentadienyl) [Ph4C4Si(Me/Cl)-(Me/Cl)SiC4Ph4] from Silole Anion − + + [MeSiC4Ph4] •[Li or Na ] and Silole Dianion 2− + [SiC4Ph4] •2[Li ]; Oxidative Coupling of Silole − + + Anion [MeSiC4Ph4] •[Li or Na ] by Ferrous Chloride (FeCl2) and Oxidative Coupling and 2− + Chlorination of Silole Dianion [SiC4Ph4] •2[Li ] by Cupric Chloride (CuCl2) Jang-Hwan Hong Department of Nanopolymer Material Engineering, Pai Chai University, 155-40 Baejae-ro (Doma-Dong), Seo-Gu, Daejon 302-735, Korea; [email protected]; Tel.: +82-42-520-5755 Academic Editor: Arnaud Gautier Received: 20 September 2019; Accepted: 15 October 2019; Published: 19 October 2019 Abstract: A reaction of silole anion {[MeSiC Ph ] [Li+ or Na+](1) with anhydrous ferrous chloride 4 4 −• (FeCl2) in THF (tetrahydrofuran) gives 1,10-bis(1-methyl-2,3,4,5-tetraphenyl-1-silacyclopentadienyl) [Ph4C4Si(Me)-(Me)SiC4Ph4](2) with precipitation of iron metal in high yield. Silole dianion {[SiC Ph ]2 2[Li+](3) is added to anhydrous cupric chloride (CuCl ) in THF at 78 C, then the 4 4 −• 2 − ◦ dark red solution changes into a greenish solution. From the solution, a green solid is isolated, and stirring it in toluene at room temperature provides quantitatively 1,10-bis(1-chloro-2,3,4,5- tetraphenyl-1-silacyclopentadienyl) [Ph4C4Si(Cl)-(Cl)SiC4Ph4](4) with precipitation of copper metal in 2 toluene. The green solid is suggested to be 1,10-bissilolyl bisradical [Ph4C4Si-SiC4Ph4] • (8), and lithium cuprous chloride salts {[Li CuICl ]+ [CuICl ] }. Both reactions are initiated by single-electron transfer 2 2 • 2 − (SET) from the electron-rich anionic silole substrates (1 and 3) to iron(II) and copper(II). Keywords: silole; anion; dianion; oxidation; oxidative-chlorination; SET (single-electron transfer); cupric chloride; ferrous chloride 1. Introduction Recent decades have witnessed tremendous progress in the field of group 14 metallole dianions and the related metallole anions [1–6] since the first silole dianion and germole dianion were reported [7,8]. 1 In particular, the syntheses and characterizations of the silole anion [1-tert-butyl-SiC4Ph4] −, the silole 2 2 2 dianion [SiC4Ph4] −, the bissilole dianion [Ph4C4Si-SiC4Ph4] −, and the germole dianion [GeC4Ph4] − as aromatic compounds [8–10], previously considered merely as intangible intermediates, have been the starting point for exploring the synthetic, theoretical, and materials chemistry of group 14 metalloles and their anions [11–27], with increasing ASE (Aromatic Stabilization Energy) of the η5-lithium salts 2 + [C4H4E] − 2[Li ][16,17]. • 2 2 Very recently, conspicuous silole dianions {[SiC2(SiMe3)2C2Ph2] −, SiC2(SiEt3)2C2Ph2] −}, silole anion 1 2 {[1-mesityl-SiC2(SiMe3)2C2Ph2] −}, and bissilole dianion {[Ph2C2(Me3Si)2C2Si-SiC2(SiMe3)2C2Ph2] −} Molecules 2019, 24, 3772; doi:10.3390/molecules24203772 www.mdpi.com/journal/molecules MoleculesMolecules 2019 2019, ,24 24, ,x x 22 ofof 1010 Molecules 2019, 24, 3772 2 of 10 2 3 2 2 2 2− 2 3 2 2 2 2− VeryVery recently,recently, conspicuousconspicuous silolesilole dianionsdianions {[SiC{[SiC2(SiMe(SiMe3))2CC2PhPh2]2]−, , SiCSiC2(SiEt(SiEt3)2)CC2PhPh2]]2−},}, silolesilole 2 3 2 2 2 1− 2 2 3 2 2 anionanion {[1-mesityl-SiC{[1-mesityl-SiC2(SiMe(SiMe3))2CC2PhPh2]1]−},}, andand bissilolebissilole dianiondianion {[Ph{[Ph2CC2(Me(Me3Si)Si)2CC2Si-Si- were reported as having2− enhanced aromatic electronic structures, due to their trialkylsilyl groups on two SiC2(SiMe3)2C2Ph2]2− } were reported as having enhanced aromatic electronic structures, due to their SiCα-carbons2(SiMe3 of)2C the2Ph silole2] } were rings reported [28–31]. as having enhanced aromatic electronic structures, due to their trialkylsilyl groups on two α-carbons of the silole rings [28–31]. trialkylsilylDuring groups the past on three two α decades,-carbons allof the of thesilole group rings 14 [28–31]. metallole and bismetallole dianions, from During the past three decades, all of the group 14 metallole and bismetallole dianions, from siliconDuring to lead, the havepast three been exploreddecades, all as of readily the group available 14 metallole highly aromatic and bismetallole systems [dianions,5,6], since from the silicon to lead, have been explored as readily available highly aromatic systems [5,6], since the siliconfollowing to mesomericlead, have structuresbeen explored have hadas readily been suggested available tohighly denote aromatic their electronic systems characteristics [5,6], since the in following mesomeric structures have had been suggested to denote their electronic characteristics in followingthe pioneering mesomeric works structures (Figure1)[ have8–10]. had been suggested to denote their electronic characteristics in thethe pioneering pioneering works works (Figure (Figure 1) 1) [8–10]. [8–10]. 2-2- 2-2- 2-2- 2-2- 2-2- 2-2- EE EE EE EE EE EE a b c d e f a b c d e f FigureFigure 1. 1. Mesomeric MesomericMesomeric structures structuresstructures of of group group 14 14 metalloles metalloles dianions. dianions. Nowadays,Nowadays, even even group group 13 13 dilithio dilithio metallolesmetalloles dianion dianion and and dilithiodilithio transitiontransition metalloles metalloles are are preparedprepared and and characterized characterized as as aromatic aromatic dianiondianion dianion metallolesmetalloles metalloles [[32]. 32[32].]. InIn general,general, reactions reactions of of silole silole anionsanions andand silolesilole dianionsdianions withwith electrophileselectrophiles areare nucleophilicnucleophilic additionsadditions to toto E E atoms atoms atoms of of of E–X E–X E–X bonds bonds bonds in in inthe the the electrophile electrophile electrophiles,s,s, to to make make to make new new new Si–E Si–E Si–Ebonds bonds bonds (E=C, (E=C, (E Si, Si,= C,Ge, Ge, Si, Sn, Sn, Ge, X=Cl, X=Cl, Sn, Br,XBr,= Cl,I) I) [1–5]. Br,[1–5]. I) [In 1In– 5the the]. Incase case the of caseof the the of silole silole the siloledianion, dianion, dianion, the the respective respective the respective reaction reaction reaction pathway pathway pathway depends depends depends on on what what on what the the electrophiletheelectrophile electrophile is—for is—for is—for example, example, example, dichlorocyclopropa dichlorocyclopropa dichlorocyclopropane,ne,ne, diphenylcyclopropeno diphenylcyclopropeno diphenylcyclopropenone,ne,ne, 2-adamantanone, 2-adamantanone, 2-adamantanone, 1,3- 1,3- 1,3-butadienes,butadienes,butadienes, and and andN N,N,NN’-di-’-di-,N0tert-di-tert-butylethylenediimine—due-butylethylenediimine—duetert-butylethylenediimine—due to to the the to presence presence the presence of of two two of anionic anionic two anionic electron electron electron pairs pairs [33–37].pairs[33–37]. [33 Nevertheless, –Nevertheless,37]. Nevertheless, all all of of them allthem of themhave have been havebeen initiated beeninitiated initiated by by formal formal by formal two-electron two-electron two-electron transfer. transfer. transfer. − ++ ++ Here,Here, wewe reportreport twotwo oxidation oxidation reactions reactions ofof silole silole anion anion [MeSiC [MeSiC4Ph4Ph4]4]− •[Li[Li+ or NaNa+ ] withwith ferrousferrous Here, we report two oxidation reactions of silole anion [MeSiC4Ph4] •[Li• or Na ] with ferrous 22− ++ chloridechloride (FeCl (FeCl2)2) andand silole silole dianion dianion [SiC[SiC44PhPh44]]2−−•2[Li2[Li+ ] ]((11)) with with cupric cupric chloride (CuCl(CuCl22). To date,date, therethere chloride (FeCl2) and silole dianion [SiC4Ph4] •2[Li• ] (1) with cupric chloride (CuCl2). To date, there areare nono reports reports onon on thethe the single-electronsingle-electron single-electron oxidationoxidation oxidation and and/or and/or/or chlorination chlorination chlorination of of of them, them, them, as as as far far far as as as we we we know. know. know. This This This is the first report for oxidative chlorination of silole dianion with cupric chloride (CuCl )2 through a isis the the first first report report for for oxidative oxidative chlorination chlorination of of silole silole dianion dianion with with cupric cupric chloride chloride (CuCl (CuCl22)) through through a a radicalradical silole silole moiety, moiety, viavia via twotwo two single-electronsingle-electron single-electron transfers.transfers. transfers. 2. Results 2.2. Results Results + + The addition of silole anion salt [MeSiC4 44Ph− 4]− +[Li or+ Na ](1) to pale brown anhydrous TheThe addition addition of of silole silole anion anion salt salt [MeSiC [MeSiC4PhPh4]]−•[Li•[Li+• or or Na Na+]] ( (11)) to to pale pale brown brown anhydrous anhydrous ferrous ferrous ferrous chloride2 (FeCl2) in THF with stirring, immediately changed a dark violet solution into chloridechloride (FeCl (FeCl2)) in in THF THF with with stirring, stirring, immediately immediately changed changed a a dark dark violet violet solution solution into into a a black black solution, solution, a black solution, with precipitation of black particles at room temperature. From the reaction withwith precipitationprecipitation ofof blackblack particlesparticles atat roomroom temperature.temperature. FromFrom thethe reactionreaction mixture,mixture, 1,11,1′-bis(1-′-bis(1- mixture, 1,10-bis(1-methyl-2,3,4,5-tetraphenyl-1-silacyclopentadienyl)4 4 [Ph44C44Si(Me)-(Me)SiC4Ph4] methyl-2,3,4,5-tetraphenyl-1-silacyclopentadienyl)methyl-2,3,4,5-tetraphenyl-1-silacyclopentadienyl) [Ph[Ph4CC4Si(Me)-(Me)SiCSi(Me)-(Me)SiC4PhPh4] ] (2(2)) waswas obtainedobtained (2) was obtained quantitatively, and the black particle was identified
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