Page 5 of 8
Please Cꢀ dh oe ꢀ mn oi ct aꢀ al dS cj ui es nt ꢀcme arginsꢀ
JournalꢀNameꢀ
ꢀARTICLEꢀ
ChemCatChem.,ꢀ 2018,ꢀ 10,ꢀ 4213;ꢀ (d)ꢀ ,ꢀ ,ꢀ
019,ꢀ363,ꢀ479;ꢀ(e)ꢀA.ꢀS.ꢀS.ꢀWilson,ꢀM.ꢀS.ꢀHill,ꢀM.ꢀF.ꢀMahon,ꢀC.ꢀ
DO 10.10 9SC01192G
R. ꢀI :L.ꢀ M e3 9l e/ Cn Science
2
Dinoiꢀ andꢀ L.ꢀ Maron,ꢀ Science,ꢀ 2017,ꢀ 358,ꢀ 1168;ꢀ (f)ꢀ F.-G.ꢀ
FontaineꢀandꢀE.ꢀRochette,ꢀAcc.ꢀChem.ꢀRes.,ꢀ2018,ꢀ51,ꢀ454;ꢀ(g)ꢀ
J.ꢀHicks,ꢀP.ꢀVasko,ꢀJ.ꢀM.ꢀGoicoecheaꢀandꢀS.ꢀAldridge,ꢀNature,ꢀ
2
018,ꢀ557,ꢀ92;ꢀ(h)ꢀY.ꢀWang,ꢀA.ꢀKostenko,ꢀT.ꢀJ.ꢀHadlington,ꢀM.-
P.ꢀ Luecke,ꢀ S.ꢀ Yao,ꢀ M.ꢀ Driess,ꢀ J.ꢀ Am.ꢀ Chem.ꢀ Soc.ꢀ 2019,ꢀ 141,ꢀ
26.ꢀ
6
2
3
M.-A.ꢀLégaré,ꢀG.ꢀBélanger-Chabot,ꢀR.ꢀD.ꢀDewhurst,ꢀE.ꢀWelz,ꢀI.ꢀ
Krummenacher,ꢀ B.ꢀ Engelsꢀ andꢀ H.ꢀ Braunschweig,ꢀ Science,ꢀ
2
018,ꢀ359,ꢀ896.ꢀ
(a)ꢀK.ꢀA.ꢀMiller,ꢀT.ꢀW.ꢀWatson,ꢀJ.ꢀE.ꢀBender,ꢀM.ꢀM.ꢀBanaszakꢀ
HollꢀandꢀJ.ꢀW.ꢀKampf,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ2001,ꢀ123,ꢀ982;ꢀ(b)ꢀ
Y.ꢀPeng,ꢀB.ꢀD.ꢀEllis,ꢀX.ꢀWangꢀandꢀP.ꢀP.ꢀPower,ꢀJ.ꢀAm.ꢀChem.ꢀ
Soc.,ꢀ2008,ꢀ130,ꢀ12268;ꢀ(c)ꢀY.ꢀPeng,ꢀJ.-D.ꢀGuo,ꢀB.ꢀD.ꢀEllis,ꢀZ.ꢀ
Zhu,ꢀJ.ꢀC.ꢀFettinger,ꢀS.ꢀNagaseꢀandꢀP.ꢀP.ꢀPower,ꢀJ.ꢀAm.ꢀChem.ꢀ
Soc.,ꢀ2009,ꢀ131,ꢀ16272;ꢀ(d)ꢀS.ꢀK.ꢀMandalꢀandꢀH.ꢀW.ꢀRoesky,ꢀ
Acc.ꢀChem.ꢀRes.,ꢀ2011,ꢀ45,ꢀ298;ꢀ(e)ꢀK.ꢀInomata,ꢀT.ꢀWatanabe,ꢀ
Y.ꢀ Miyazakiꢀ andꢀ H.ꢀ Tobita,ꢀ J.ꢀ Am.ꢀ Chem.ꢀ Soc.,ꢀ 2015,ꢀ 137,ꢀ
11935;ꢀ(f)ꢀA.ꢀV.ꢀProtchenko,ꢀJ.ꢀI.ꢀBates,ꢀL.ꢀM.ꢀA.ꢀSaleh,ꢀM.ꢀP.ꢀ
Blake,ꢀA.ꢀD.ꢀSchwarz,ꢀE.ꢀL.ꢀKolychev,ꢀA.ꢀL.ꢀThompson,ꢀC.ꢀJones,ꢀ
P.ꢀMountfordꢀandꢀS.ꢀAldridge,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ2016,ꢀ138,ꢀ
ꢀ
Me
Fig.ꢀ 6.ꢀ Molecularꢀstructureꢀofꢀ( IPrCH)SiH(CN){Si(SiMe
3
)
3
}ꢀ (7)ꢀwithꢀthermalꢀellipsoidsꢀ
plottedꢀatꢀaꢀ30ꢀ%ꢀprobabilityꢀlevel.ꢀAllꢀhydrogenꢀatomsꢀ(exceptꢀtheꢀvinylicꢀandꢀsilicon-
boundꢀhydrogens)ꢀwereꢀomittedꢀforꢀclarity.ꢀSelectedꢀbondꢀlengthsꢀ[Å]ꢀandꢀanglesꢀ[°]:ꢀ
C4-Si1ꢀ1.709(3),ꢀSi1-H1ꢀ1.46(5),ꢀSi1-Si2ꢀ2.3396(15),ꢀSi1-C5ꢀ1.918(5),ꢀC5-N2ꢀ1.110(7);ꢀC4-
S1-Si2ꢀ116.64(10),ꢀC4-Si1-C5ꢀ111.9(2),ꢀSi1-C5-N2ꢀ175.0(6).ꢀꢀ
4
555;ꢀ (g)ꢀ M.ꢀ M.ꢀ D.ꢀ Roy,ꢀ S.ꢀ Fujimori,ꢀ M.ꢀ J.ꢀ Ferguson,ꢀ R.ꢀ
Conclusionsꢀ
McDonald,ꢀN.ꢀTokitohꢀandꢀE.ꢀRivard,ꢀChem.ꢀEur.ꢀJ.,ꢀ2018,ꢀ24,ꢀ
14392;ꢀ (h)ꢀ T.ꢀ J.ꢀ Hadlington,ꢀ M.ꢀ Driessꢀ andꢀ C.ꢀ Jones,ꢀ Chem.ꢀ
Soc.ꢀRev.,ꢀ2018,ꢀ47,ꢀ4176.ꢀ
Inꢀ thisꢀ work,ꢀ theꢀ synthesisꢀ ofꢀ aꢀ thermallyꢀ stable,ꢀ two-
Me
coordinateꢀ acyclicꢀ silyleneꢀ
achieved,ꢀandꢀisꢀtheꢀfirstꢀexampleꢀofꢀsuchꢀaꢀspeciesꢀsupportedꢀ
byꢀ aꢀ carbon-basedꢀ ligand.ꢀ Theꢀ stabilizingꢀ influenceꢀ ofꢀ
3 3
( IPrCH)Si{Si(SiMe ) }ꢀ wasꢀ
4
5
(a)ꢀ Y.ꢀ Mizuhata,ꢀ T.ꢀ Sasamoriꢀ andꢀ N.ꢀ Tokitoh,ꢀ Chem.ꢀ Rev.,ꢀ
2
009,ꢀ109,ꢀ3479;ꢀ(b)ꢀM.ꢀAsay,ꢀC.ꢀJonesꢀandꢀM.ꢀDriess,ꢀChem.ꢀ
Rev.,ꢀ2011,ꢀ111,ꢀ354;ꢀ(c)ꢀE.ꢀRivard,ꢀChem.ꢀSoc.ꢀRev.,ꢀ2016,ꢀ45,ꢀ
989.ꢀ
Me −
IPrCH] ꢀwasꢀevaluatedꢀexperimentallyꢀandꢀcomputationally.ꢀ
[
Theꢀhighꢀreactivityꢀofꢀthisꢀnewꢀsilyleneꢀwasꢀdemonstratedꢀbyꢀ
itsꢀ roomꢀ temperatureꢀ activationsꢀ ofꢀ strongꢀ homo-ꢀ andꢀ
heteroatomicꢀbonds.ꢀFutureꢀworkꢀwillꢀtargetꢀtheꢀsynthesisꢀofꢀ
(a)ꢀ P.ꢀ Jutzi,ꢀ U.ꢀ Holtmann,ꢀ D.ꢀ Kanne,ꢀ C.ꢀ Krüger,ꢀ R.ꢀ Blom,ꢀ R.ꢀ
GleiterꢀandꢀI.ꢀHyla-Kryspin,ꢀChem.ꢀBer.,ꢀ1989,ꢀ122,ꢀ1629;ꢀ(b)ꢀ
H.ꢀ H.ꢀ Karsch,ꢀ U.ꢀ Keller,ꢀ S.ꢀ Gamperꢀ andꢀ G.ꢀ Müller,ꢀ Angew.ꢀ
Chem.ꢀInt.ꢀEd.ꢀEngl.,ꢀ1990,ꢀ29,ꢀ295;ꢀ(c)ꢀM.ꢀKumarꢀBisai,ꢀV.ꢀS.ꢀ
V.ꢀ S.ꢀ V.ꢀ S.ꢀ N.ꢀ Swamy,ꢀ T.ꢀ Das,ꢀ K.ꢀ Vankaꢀ andꢀ R.ꢀ G.ꢀ Gonnade,ꢀ
Inorg.ꢀChem.,ꢀ2019,ꢀDOI:ꢀ10.1021/acs.inorgchem.9b00418.ꢀ
M.ꢀDenk,ꢀR.ꢀLennon,ꢀR.ꢀHayashi,ꢀR.ꢀWest,ꢀA.ꢀV.ꢀBelyakov,ꢀH.ꢀP.ꢀ
Verne,ꢀA.ꢀHaaland,ꢀM.ꢀWagnerꢀandꢀN.ꢀMetzler,ꢀJ.ꢀAm.ꢀChem.ꢀ
Soc.,ꢀ1994,ꢀ116,ꢀ2691.ꢀ
(a)ꢀB.ꢀD.ꢀRekken,ꢀT.ꢀM.ꢀBrown,ꢀJ.ꢀC.ꢀFettinger,ꢀH.ꢀM.ꢀTuononenꢀ
andꢀP.ꢀP.ꢀPower,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ2012,ꢀ134,ꢀ6504;ꢀ(b)ꢀA.ꢀV.ꢀ
Protchenko,ꢀ K.ꢀ H.ꢀ Birjkumar,ꢀ D.ꢀ Dange,ꢀ A.ꢀ D.ꢀ Schwarz,ꢀ D.ꢀ
Vidovic,ꢀ C.ꢀ Jones,ꢀ N.ꢀ Kaltsoyannis,ꢀ P.ꢀ Mountfordꢀ andꢀ S.ꢀ
Aldridge,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ2012,ꢀ134,ꢀ6500.ꢀꢀꢀ
Me
−
moreꢀ nucleophilicꢀ sourcesꢀ ofꢀ [ IPrCH] ꢀ whichꢀ mayꢀ allowꢀ forꢀ
theꢀ formationꢀ ofꢀ aꢀ stableꢀ divinylsilyleneꢀ andꢀ relatedꢀ reactiveꢀ
speciesꢀforꢀmainꢀgroupꢀelement-basedꢀcatalysis.ꢀ
6
7
Conflictsꢀofꢀinterestꢀ
Thereꢀareꢀnoꢀconflictsꢀtoꢀdeclareꢀ
8
9
M.ꢀJ.ꢀS.ꢀGynane,ꢀD.ꢀH.ꢀHarris,ꢀM.ꢀF.ꢀLappert,ꢀP.ꢀP.ꢀPower,ꢀP.ꢀ
RiviѐreꢀandꢀM.ꢀRiviѐre-Baudet,ꢀJ.ꢀChem.ꢀSoc.,ꢀDaltonꢀTrans.,ꢀ
Acknowledgementsꢀ
1
977,ꢀ2004.ꢀ
E.R.ꢀ thanksꢀ theꢀ NSERCꢀ ofꢀ Canadaꢀ forꢀ Discoveryꢀ andꢀ CREATEꢀ
grants,ꢀ theꢀ Canadaꢀ Foundationꢀ forꢀ Innovation,ꢀ andꢀ theꢀ
UniversityꢀofꢀAlberta,ꢀFacultyꢀofꢀScienceꢀ(ResearchꢀAward)ꢀforꢀ
funding.ꢀ Theꢀ computationalꢀ studiesꢀ inꢀ thisꢀ workꢀ wereꢀ madeꢀ
possibleꢀ byꢀ theꢀ facilitiesꢀ ofꢀ Compute/Calculꢀ Canadaꢀ
(a)ꢀA.ꢀV.ꢀProtchenko,ꢀA.ꢀD.ꢀSchwarz,ꢀM.ꢀP.ꢀBlake,ꢀC.ꢀJones,ꢀN.ꢀ
Kaltsoyannis,ꢀ P.ꢀ Mountfordꢀ andꢀ S.ꢀ Aldridge,ꢀ Angew.ꢀ Chem.ꢀ
Int.ꢀEd.,ꢀ2013,ꢀ52,ꢀ568;ꢀ(b)ꢀT.ꢀJ.ꢀHadlington,ꢀJ.ꢀA.ꢀB.ꢀAbdalla,ꢀR.ꢀ
Tirfoin,ꢀS.ꢀAldridgeꢀandꢀC.ꢀJones,ꢀChem.ꢀCommun.,ꢀ2016,ꢀ52,ꢀ
1717;ꢀ (c)ꢀ D.ꢀ Wendel,ꢀ A.ꢀ Porzelt,ꢀ F.ꢀ A.ꢀ D.ꢀ Herz,ꢀ D.ꢀ Sakar,ꢀ C.ꢀ
Jandl,ꢀS.ꢀInoueꢀandꢀB.ꢀRieger,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ2017,ꢀ139,ꢀ
(
www.computecanada.ca).ꢀ Weꢀ thankꢀ Dr.ꢀ Paulꢀ Lummisꢀ forꢀ
8
134;ꢀ(d)ꢀY.ꢀK.ꢀLoh,ꢀL.ꢀYing,ꢀM.ꢀÁ.ꢀFuentes,ꢀD.ꢀC.ꢀH.ꢀDoꢀandꢀS.ꢀ
preliminaryꢀexperimentalꢀinvestigationsꢀandꢀDr.ꢀEmanuelꢀHupfꢀ
forꢀ helpfulꢀ discussions.ꢀ Mr.ꢀ Markꢀ Miskolzieꢀ isꢀ gratefullyꢀ
Aldridge,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.,ꢀ2019,ꢀ58,ꢀ4847.ꢀ
0 Aꢀcyclicꢀdialkylsilyleneꢀhasꢀbeenꢀpreviouslyꢀreported:ꢀM.ꢀKira,ꢀ
S.ꢀIshida,ꢀT.ꢀIwamotoꢀandꢀC.ꢀKabuto,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ1999,ꢀ
121,ꢀ9722.ꢀ
1 (a)ꢀ C.ꢀ Hering-Junghans,ꢀ P.ꢀ Andreiuk,ꢀ M.ꢀ J.ꢀ Ferguson,ꢀ R.ꢀ
McDonaldꢀ andꢀ Eꢀ Rivard,ꢀ Angew.ꢀ Chem.ꢀ Int.ꢀ Ed.,ꢀ 2017,ꢀ 56,ꢀ
1
1
29
acknowledgedꢀ forꢀ hisꢀ assistanceꢀ acquiringꢀ Siꢀ andꢀ variableꢀ
temperatureꢀNMRꢀspectraꢀandꢀProf.ꢀAlexꢀBrownꢀforꢀhisꢀhelpfulꢀ
discussionsꢀrelatingꢀtoꢀtheꢀcomputationalꢀworkꢀpresented.ꢀWeꢀ
alsoꢀthankꢀMr.ꢀSamuelꢀBairdꢀforꢀcreatingꢀtheꢀTOCꢀgraphic.ꢀE.R.ꢀ
thanksꢀtheꢀAlexanderꢀvonꢀHumboldtꢀFoundationꢀforꢀfellowship.ꢀ
6
272;ꢀ (b)ꢀ Forꢀ anꢀ exampleꢀ ofꢀ aꢀ base-stabilizedꢀ
divinylgermylene,ꢀsee:ꢀM.ꢀWalewska,ꢀJ.ꢀBaumgartnerꢀandꢀC.ꢀ
Marschner,ꢀChem.ꢀCommun.,ꢀ2015,ꢀ51,ꢀ276.ꢀ
1
2 ForꢀreviewsꢀonꢀNHOꢀligands,ꢀsee:ꢀ(a)ꢀR.ꢀS.ꢀGhadwal,ꢀDaltonꢀ
Trans.,ꢀ2016,ꢀ45,ꢀ16081;ꢀ(b)ꢀR.ꢀD.ꢀCrockerꢀandꢀT.ꢀV.ꢀNguyen,ꢀ
Chem.ꢀEur.ꢀJ.,ꢀ2016,ꢀ22,ꢀ2208;ꢀ(c)ꢀM.ꢀM.ꢀD.ꢀRoyꢀandꢀE.ꢀRivard,ꢀ
Acc.ꢀChem.ꢀRes.,ꢀ2017,ꢀ50,ꢀ2017.ꢀ
Notesꢀandꢀreferencesꢀ
1
Forꢀ recentꢀ reviewsꢀ andꢀ articles,ꢀ see:ꢀ (a)ꢀ T.ꢀ Chuꢀ andꢀ G.ꢀ I.ꢀ
Nikonov,ꢀ Chem.ꢀ Rev.,ꢀ 2018,ꢀ 118,ꢀ 3608;ꢀ (b)ꢀ P.ꢀ P.ꢀ Power,ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ5ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ