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The Use of Sterically Bulky Phosphine Ligands in Iron and Ruthenium Dinitrogen Chemistry

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The Use of Sterically Bulky Phosphine Ligands in Iron and Ruthenium Dinitrogen Chemistry The Use of Sterically Bulky Phosphine Ligands in Iron and Ruthenium Dinitrogen Chemistry A thesis submitted in partial fulfilment of the requirements for admission to the degree of Doctor of Philosophy by Ryan James Gilbert-Wilson School of Chemistry The University of New South Wales Australia PLEASE TY!'E Tli~ UNIVERSITY OF NeW SOUTH W.li..ES Tll.. l a/Dlsaemotlon Sh"t 5umame 01 fam~ name: GilllM·Wi~On Ftrat name. Ry•n 01her namm JameO AbbreYlllfon tor d<lgiM a• Qlii!Jf1 llllho UniVo,.I\Y calelldar. PhO Sdlb<ll Cnem11lry Tille: The Uoe Ol Sto~t<~lly Bulky Pho~~nlnc l l!iOridsln lrun ana Rlltllentum Olnltnlgflll Cll<lrnlob) Ab$traet350 .,.,_ muimum: (PLEASE TYPE) This ll;esls Is pmranly oonc:emoa with 111• dovalopmenl of new muHidcnlQto photphlnellgands, the synthesis anc unodlona ol tron and ruthenium compl=s ot ~e llgllllds, With a •pec:illc toc:w on tho comp!eXoo wnl<:h IMOIJ)Orate 1 dlnlltogellllgano~ All mettl COfi!Piexea wo1o cf1araderlzlld DY ml{ltlnU<Jtell NMR SOOct!O$CQpY and twonty threa single crystal X-ray structure& ol new complexes wore deta...,ln<ld Tho synl!losls anc dlamCIDiiilillo~ of the ktndered tnpodel phMphlne ligand P(CH,CH,CI'IJP'Pr1)-o (P'P/") Is dosct,oed, oloi\Q wltn lh• •ynlhoala and oha111ctell<illlon ofiRuC~P'P,'Pr)HIIPII.J Ruii,(P'Pa'Pr), and IR\IIH,)(H)(P'P,"')J(BPII.) (RuCI(P'P,'Pr)JIBPII.ojts ftuiUOnalln aotu!lon,.u1c IDW tomoo"•lllra NMR specuascopY of lhe comp.le¥ cor1111ates well w)th two dynamic pto<:Mses. The oynthestS 8nd ohorJ<:te rtu~OII ol tno extremely hinder«! phosphine llgollda1 P(CH1CH,P'eu,), (P'P>'""), PhP(C:H,CH,P'Ilu,), (PhP'Pi''l. and P(CH,Cf1,CH,P'eu,)J (P'P,""') aro 6Cs0tlbe(j, atong wrl!llhe syntllos<s ol 111111 nlll\onrum cjiiQro """'Jllexu The DUiky P'P,.. and P'P,""IIQJnds are tile mostarer'ocally encumber.., PP.-type ligands so syni!II!Sizod and In •II .,.... only three p~oaphorus donora a"' abl<llo bind 1o the metal centre. Low lempcr.llut• SOiu!lO!Iand celld state "P('HI NMR wote uoed to demonahote the un~""""' olrvc:tvre of !1uCI,(P1P,0 Ttll#lrnont at RuCI1(P'P,-., \!Mh • ••rtety ot hydride transfer agents ollorde<t four new Nthontum llydti<IM "The tulnonium compj-. Y!ilh omall molecule dono!"$ RuH>(CO)(P'P,•), RuHI(N!)(P'P,"'), RuH,(H,)(P'P,""'). RlJHCi(CO)(P'P,., and RuHC ~N-,I(P'P,.., were lllaoaymh011nd. Tho "N complo•, RuH.("Nt){P'P,-.,1was also synthesiled ond otuQiod The synthM1s c.t a Htlea Of tron ana tVlhtmum complfutei 'Mih "'" tlg-n(l P~.or. (P{CH,Ct'I;~PCy2}J) l$ Qft$ctlbttG lh61tOn(U). ru.thfUltutn(O), and tron(l) dlnltrogen tQITIPteus f'e(N,}(P7P,••), Ru(N,)(P'P..,), 2nd lft(N,)(P'p,<>jj" •nd tile !UIIIInlum(l) ohlcnl ccmplex RuC~P'P,") wota -synl!leiiZed "tfeductlon ~n<fer a nl~en at~MSPhero . Thelton(ll) ccmpf•• Fe(H•)(P'P,"') was -'•o oyn\hoslzed Tho cattonlc dlnlltog$n ·~ (l'e(N1)H(P'P,~)J' and ~u(N1)H!P'P, 'll' were prep•••d by treolrnont ol and reapedlvely, wrth ona oqutv ot a wellk O<gantc ac:>d The synl!le$1S and onara«ertzatlon ollh& ~m9n centered pod and ligand precumr "C'P,., Is ducnbed. A mol!lod tor tile lonnot~n ol "'lhenlum hydnde compleXes w1tn carn<m centered podancals dev,fc)ped, uUtll.fng • ructiOn ol hotwun r~tnenlum dl~)'d11de contp!o>es wdh mo llga!id preoul$0t. "c'P.''' This ""'tho<II'S used to produce 111<>rVIhOl11um complel<eo Rui'I(CO)ic'll.'''l•nd RuH(fol,)(c'r>,"') Attomp!Atd reacllon• of RuH(N,j(c'P.''') ._,., t lao dcstlibeU. Ooolal'lt!OI' f'O!lltlng to <IISPCM~I!k>'l or pro)tot tnests/dtsconatton I heroby g11111t to 1111 University ot New Soutll W"los or II• "ffORis IIIII rtghl to an:h!vo one to mar.. IMIIIIbla my thesis or dr818rti!Mn In wholo or'" panln tne University libranoa In all rorm• ol m~dla, now or llere aner knO\Yfl, subjoclto I~• provfslono of Inc Copyrighj 1\Q 11168 I reloln • II ~tliPOIIY ttg~tt . >UCh •• oatontrt~~nta. l•lso totoln tnc ~~gntto vse In Mu"' we<n(W<lll a.s anlele$ or OOOI<SIGII oroan ol thl$11!eel$ or Ol$$0na~on I o!so oulhor1sc Unlu.mty Mlorofilms to usc tho 350 WOld ob1~ct of my lhlffialn 016o<tn.llon Nl<>IT11GIS lnlematlonal (!!•is IS •ppOeablo to do<:taral UICSS$ only), /~ .A .... ~~;3 '.)J.. ..... --~ ~ ·--·- ~ -- ~~ Wltna.. lo.ta l'lle Umversrly 'I!GOQ"""'•thatlll•"' may be """"pl•oo•l circumstances reQlllnnr;ll!SJtldiQns on ~pflng or condtUons on use, Reqoosta tor mtlfr:t.an f~r • ponoo or up to 2 years 111ust ca nr8de m wrtung . ll,quuw for a longer petloct uf tellr(ctJon may be consldel'l!d 1~ excuptttmel circumstances and IMUire till a""""""l ol the Oeon .ol Graduate Resoardl FOR OFl'fCE"USii ONLY Oats or completion of rnqullt!llt~nft for Award THIS S~EET IS TO BE GLUED TO lll£ INSlDE FRONT COVER Of llll: lllESIS COPYRIGHT STATEMENT 'I hereby g1rant lhe Unlvernfty of New South Wales or Its agents the right to archive and t.o make available my lhesls or dlsse111!tlon In whole or part In the University nbraries In all forms of media, now or hBrB after known, Sllbject to the provisions t•f lhe Copyright Act 1968. I retain all proprfetary rights, SlJCh as patent rights. I also relafn lhe right to use In future worl<s (such as artldes or books) all or part of litis thesis or dlssert;ltion. I also authorise UniVersity Microfilms to use the 350 word abstrnct of my thesis in Dissertation! AbstractlnternaUonal (lhis ls appl1cable 10 doctorallheses only). 1 hove elthE•r used no substantlal portions of copyright material tn my thesis or I have obtained permission to use copyright material; Where permission has not been glant<Kl I have applied/will apply lor a partial rasllicllon of the digital copy of my thesis or dissertation.' f{ I' - ' Signed ... ·····l.fi' .. l.-.9.H .:7 ~................. .. Date .... 4.~./3. .}11 .............................................. AUniENTliCITY STATEMENT 'I Cl!rtil)t lhat the Llbrary deposit digital copy is a direct equivalent or the final o~ally approved version of my thosls. No emendation or contentllas oc:cu:rred and If ther'e am any mtnor var1aUo11s ln formatting, they are the result of the c;onverslon to digital formaL' Signed .... ~~····--~~·~··· "··.. ··" Date ,,, ';?,.~.j-3 /1.3 ....................... ,.... , ..................... Certificate of Originality 'I hereby declare that this submission is my own work and to the best of my knowledge it contains no materials previously published or written by another person, or substantial proportions of material which have been accepted for the award of any other degree or diploma at UNSW or any other educational institution, except where due acknowledgement is made in the thesis. Any contribution made to the research by others, with whom I have worked at UNSW or elsewhere, is explicitly acknowledged in the thesis. I also declare that the intellectual content of this thesis is the product of my own work, except to the extent that assistance from others in the project's design and conception or in style, presentation and linguistic expression is acknowledged.' Signature: I Preface This thesis is a report of original research undertaken by the author and is submitted for admission to the degree of Doctor of Philosophy at the University of New South Wales. The work was completed in the School of Chemistry at the University of New South Wales during the period March 2009 to August 2012. The work and results presented in this thesis are those of the author, unless otherwise acknowledged. Sections of this work have been published: 1. Ruthenium Hydride Complexes of the Hindered Phosphine Ligand Tris(3-diisopropylphosphinopropyl)phosphine. Bhadbhade, M. M., Field, L. D., Gilbert-Wilson, R., Guest, R. W. and Jensen, P. Inorganic Chemistry, 2011, 50, 6220-6228. t 2. New Super-hindered Polydentate Polyphosphine Ligands P(CH2CH2P Bu2)3, t t PhP(CH2CH2P Bu2)2, P(CH2CH2CH2P Bu2)3 and their Ruthenium (II) Chloride Complexes. Gilbert-Wilson, R., Field, L. D. and Bhadbhade, M. M. Inorganic Chemistry, Accepted January 2012. Sections of this work have been presented at Scientific Conferences: 1. Iron and ruthenium hydride complexes of the novel phosphine ligand Tris(3- diisopropylphosphinopropyl)phosphine. R. Gilbert-Wilson, L. D. Field II 16th Reactive Organometallics Symposium, University of New South Wales, Sydney, June 2009. Oral Presentation. 2. The use of steric factors in the quest for nitrogen fixation by Group 8 metals with phosphine ligands. R. Gilbert-Wilson, L. D. Field 5th Australian Organometallics Meeting, (OZOM 5), University of New South Wales, Sydney, January 2010. Poster Presentation. 3 iPr 3. Iron and ruthenium hydride complexes of the novel phosphine ligand P P3 . R. Gilbert-Wilson, L. D. Field 17th Reactive Organometallics Symposium, Australian National University, Canberra, June 2010. Oral Presentation. 4. Dihydrogen Route to Ruthenium Dinitrogen Complexes. R. Gilbert-Wilson, L. D. Field 6th Australian Organometallics Meeting, (OZOM 6), University of Tasmania, Hobart, January 2011. Oral Presentation. 5. Novel sterically bulky phosphines on ruthenium: Effects on dinitrogen coordination. R. Gilbert-Wilson, L. D. Field, M. M. Bhadbhade III 1st European Association for Chemical and Molecular Sciences Inorganic Chemistry Conference (EICC-1), University of Manchester, Manchester, UK, 11th -14th April 2011.
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