Azavinylidene Complexes from Coupling Reactions of Organonitriles with Phosphines - Lee et al. - 2021 - Unknown

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pubs.acs.org/OrganometallicsArticleAzavinylideneComplexesfromCouplingReactionsofOrganonitrileswithPhosphines††Kui-FunLee,TilongYang,Long-YiuTsang,HermanH.Y.Sung,IanD.Williams,*ZhenyangLin,*andGuochenJia*CiteThis:Organometallics2021,40,358−369ReadOnlineACCESSMetrics&MoreArticleRecommendations*sıSupportingInformationABSTRACT:Thereactionsoftherhenium(III)-phosphinecomplexReCl3(PMePh2)3withorganonitriles(NCR)werestudiedandfoundtogivenoveladditionaswellassimplesubstitutionproducts.RefluxingReCl3(PMePh2)3inacetonitrile(MeCN)yieldedamixtureoftheorganonitrilerheniumcomplexReCl3(PMePh2)2(NCMe)andtherheniumphosphonium-substitutedazavinylidenecomplexReCl3(PMePh2)2{NC(PMePh2)-Me}.Similarly,reactionsofReCl3(PMePh2)3witharylnitrilesp-R-C6H4CN(R=H,Me,andBr)gavethecorrespondingazavinylidenecomplexesReCl3(PMePh2)2{NC(PMePh2)(p-C6H4R)}.ThenitrilecomplexReCl3(PPh3)2(NCPh)isunreactivetowardexternalPPh3,butitreactswithexcessPMe3toproducetheazavinylidenecomplexReCl3(PMe3)2{NC(PMe3)Ph}.ComputationalstudiesrevealtheeffectofligandandsubstituentoforganonitrilesonthethermodynamicsandkineticsforthereactionsofReCl3(PR3)2(NCR′)withPR3.Boththeexperimentalandcomputationalresultsindicatethatnucleophilicadditionofphosphinestocoordinatednitrilesismorefavorablefornitrileswithanelectron-withdrawinggroupandforphosphineswhicharemoreelectron-donating.■INTRODUCTIONmononuclearcomplexesofthistypefromeitherreactionsoforganonitrileswithphosphinecomplexesorreactionsofPhosphinesandorganonitrilesarecommonlyusedligandsforcoordinationandorganometalliccompounds.1Theyusuallydophosphineswithorganonitrilecomplexes.notreactwitheachother,andnumerouscomplexeswithbothReportedP−Cbondformationreactionsoforganonitrilesaphosphineandanorganonitrileligandonthesamemetalmainlyinvolveinsertionofnitrilesintometal−phosphide(M−78centerareknown.WhenaphosphinereactswithanPR2),metal−iminophosphide(M−{P(NR′)R2}),and9organonitrilecomplex,substitutionofanitrileligandwithmetal−phosphinidene(MPR)bonds.SimilarP−Cbondthephosphineligandnormallyoccurs.Infact,organonitrileformationreactionsinvolvingcouplingsoforganonitrilesand10complexeshaveoftenbeenusedasconvenientstartingtertiaryphosphinesonmononuclearmetalfragmentsareverymaterialsincoordinationchemistryduetothelabilityofthescarce.Dilworthandhisco-workersfoundthatthereactionsofNCRligands.ReactionsoforganonitrileswithphosphinetheRe(V)oxocomplexes[ReOX3(PPh3)2](1,X=ClorBr)complexesusuallyoccuratasitewithoutinvolvingthemetal−withtheaminophosphinePh2PN(SiMe3)2,PPh3,andwaterinphosphinebond,oroccasionallyleadtothesubstitutionofawetMeCNgiveamixtureofReX2{NC(Me)P(O)Ph2}-DownloadedviaUNIVOFCALIFORNIASANTABARBARAonMay15,2021at17:10:15(UTC).Seehttps://pubs.acs.org/sharingguidelinesforoptionsonhowtolegitimatelysharepublishedarticles.phosphineligandbyanorganonitrileligand.Forexample,(MeCN)(PPh3)(2)andReX3(PPh3)2(MeCN)(3),presum-OsH(PiPr)reactswithNCPhtogivetheazavinylidene11632ablyviaamidointermediateA(Scheme1).Veryrecently,i2,3complexOsH3(NCPh)(PPr3)2,whereasthereactionofPeryshkovandhisco-workersdiscoveredthatTaCl5reactedRuCl2(PPh3)3withAg2SO4inasolutionofacetonitrileandwith1.14equivofPPh3and1.1equivofPhCNtogive24methanolproducesRu(η-SO4)(NCMe)2(PPh3)2.unexpectedcationicimidocomplex4,andwith2equivofIthasbeendemonstratedthatcoordinatedorganonitriles−−PPh3andexcessMeCNtogivethezwitterionicvinylimidocanbeattackedbyavarietyofnucleophilesincludingH,R,−−5complexTa{NC(PPh3)CH2}Cl4(MeCN)(5)(SchemeOR,SR,andamines.Phosphinesarealsowell-known1261).Complex4ispresumablyformedviaattackofnucleophiles.Inprinciple,annitrilecomplexLnM(NCR)+[HPPh3]onphosphoranylideneintermediateB,while5iscouldalsobeattackedbyaphosphineonthecoordinatedorganonitrileligandtogiveaphosphonium-substitutedazavinylidene(orketimide)complexLnM{NC(PR′3)R},Received:November4,2020acomplexsimilartovinylidenecomplexesLnMCCRR′Published:January20,2021displayingclose-to-linearM−N−Cgeometriesasaresultofsignificantπ-donationfromthenitrogenatomtotheemptymetalorbitals.However,tothebestourknowledge,noreportshaveappearedintheliteratureontheformationof©2021AmericanChemicalSocietyhttps://dx.doi.org/10.1021/acs.organomet.0c00704358Organometallics2021,40,358−369

1Organometallicspubs.acs.org/OrganometallicsArticleC(PMePh)Me}(8a),whichdisplayed31Psignalsat−3.7andScheme1.ReportedP−CBondFormationReactions2InvolvingPhosphinesandNitriles−37.2ppm.ThestructureofthenitrilecomplexRe-Cl3(PMePh2)2(NCMe)(7a)hasbeenconfirmedbyanX-raydiffractionstudy.AsshowninFigure1,thecomplexadoptedpresumablyformedbyattackofPPh3ontheazaalleneintermediateTa(NC=CH2)Cl4(MeCN).Inthiswork,wereportformationofphosphonium-Figure1.Crystalstructureofnitrilecomplex7a.HydrogenatomsaresubstitutedazavinylidenecomplexesReCl3(PR3)2{NC-omittedforclarity.Selectedbondlengths[Å]andangles[°]:Re(1)−(PR3)R′}fromthereactionsofReCl3(PMePh2)3withR′CNN(1)2.039(2),N(1)−C(1)1.139(3),C(1)−N(1)−Re(1)176.2(2),andthereactionsofReCl3(PPh2)3(R′CN)withexternalN(1)−C(1)−C(2)178.1(3).phosphines.■RESULTSANDDISCUSSIONanoctahedralgeometrywiththreemeridionallyboundReactionsofReCl3(PMePh2)3withNitriles.ComplexeschlorideligandsandtheMeCNligandbeingtranstooneofofthetypeReCl3(PR3)2(R′CN)areusefulprecursorsforthechlorideligands.Thecomplexadoptsageometrysimilarto13thatof[VCl(MeCN)(PPhMe)].16TheRe−Nbondcoordination/organometalliccomplexesofrhenium.The322monomericrhenium(III)complexesReCl3(PAr3)2(RCN)(Rdistancein7a(2.039(2)Å)issimilartothatoftheanalogous17=MeandPh;Ar=Ph,p-tol,andm-tol)canbepreparedincomplexReCl3(PPh3)2(NCMe)(2.068(5)Å),butitishighyieldsbyheatingReOCl3(PAr3)2withanexcessoftheappreciablyshorterthanthatofReCl153(dppe)(NCMe)correspondingtriarylphosphineandanorganonitrile.14Sim-(2.121(8)Å)inwhichthenitrileligandistranstoailarly,thecomplexReOCl3(dppe)reactswithacetonitrileinphosphineligand.Whileparamagneticcomplex7aissilentinthe31P{1H}NMRspectrum,the1HNMRspectrumshowedthepresenceofexcessoftriphenylphosphinetogivethemonomericrhenium(III)nitrilecomplexReCl3(dppe)-fivesharplinesat57.26(s,3H,NCMe),14.38(d,J=7.5Hz,(MeCN).15Ithasbeensuggestedthatthe8H,Ph),9.35(t,J=7.5Hz,4H,Ph),9.13(t,J=7.5Hz,8H,ReCl3(PR3)2(R′CN)complexesweregeneratedbythePh),and0.82(s,6H,PMePh2)ppm,consistentwiththesolid-reactionsofR′CNwithReCl3(PR3)2intermediatesderivedstatestructure.fromthereactionsofReOCl3(PR3)2withPR3.ThestructureoftheazavinylidenecomplexRe-InourattemptstopreparecomplexesofthetypeCl3(PMePh2)2{NC(PMePh2)Me}(8a)hasalsobeenReCl3(PMePh2)2(R′CN),wehavecarriedoutthereactionsdeterminedbyanX-raydiffractionstudy.AsshowninFigureofReCl3(PMePh2)3withorganonitriles.Noappreciable2,thecomplexhasacoordinationspheresimilartothatofreactionwasobservedafteramixtureofReCl3(PMePh2)3nitrilecomplex7awiththreemeridionallyboundchloride(6)and2equivalentsofMeCNintoluenewasrefluxedfor4h.ligandsandtwotrans-disposedPMePh2ligands.ThemostInterestingly,refluxingReCl3(PMePh2)3(6)inacetonitrilefor2hproducedadarkgreensolution,whichdisplayedasinglet31P{1H}signaloffreePMePhat−26.6ppmandtwosinglet231P{1H}NMRsignalsat−3.7and−37.2ppm.Byrepeatedrecrystallizations,weisolatedtwocrystallinecomplexesfromthereactionmixture.OneisorangeincolorandwasidentifiedastheparamagneticnitrilecomplexReCl3(PMePh2)2(NCMe)(7a),whichis31PNMRsilent(Scheme2).Theotherisdarkgreenincolorandwasidentifiedasthephosphonium-substitutedazavinylidenecomplexReCl3(PMePh2)2{NScheme2.ReactionsofReCl3(PMePh2)3withAcetonitrileFigure2.Crystalstructureofazavinylidenecomplex8a.Hydrogenatomsareomittedforclarity.Selectedbondlengths[Å]andangles[°]:Re(1)−N(1)1.789(3),N(1)−C(1)1.302(5),P(3)−C(1)1.781(3),C(1)−N(1)−Re(1)177.7(3),C(1)−N(1)−P(3)113.1(3),N(1)−C(1)−C(2)120.5(2).359https://dx.doi.org/10.1021/acs.organomet.0c00704Organometallics2021,40,358−369

2Organometallicspubs.acs.org/OrganometallicsArticleinterestingstructuralfeatureliesintheRe{NC(PMePh2)-Scheme4.ReactionsofReCl3(PMePh2)3withArylnitrilesinMe}fragment.TheRe−N−Cchainisalmostlinear(Re(1)−RefluxingTolueneN(1)−C(1),177.7(3)°).ThemultiplebondcharacteroftheReNandCNbondsisreflectedbytheshortRe−N(1.789(3)Å)andN−C(1.302(5)Å)distances.TheRe−Ndistanceisslightlyshorterthanthoseofreportedrheniumazavinylidene18−20,11complexesLnReNCR2,butitisslightlylongerthanthoseofreportedrheniumimidocomplexesLnRe21−24NR.TheC−Ndistanceisslightlylongerthanthoseof18−20,11reportedazavinylidenecomplexes.TheC(1)−Pdistance(1.781(3)Å)isappreciablylongerthanthatofthePCdoublebond(1.712(2)Å),butitisslightlyshorterthanthatoftheP−CH2singlebond(1.808(2)Å)in25Ph2PCH2PPh2C(H)C(O)C6H4-p-Br.Thestructuraldataindicatethatbothresonancestructures8a(A)and8a(B)contributetothestructureof8a,withtheformerbeingmoreimportant(Scheme3).Thus,thecomplexcanbebestdescribedasanazavinylidenecomplex.Scheme3.TwoResonanceStructuresofAzavinylideneComplexReCl3(PMePh2)2{NC(PMePh2)Me}(8a)C6H4Me)}(8c)andReCl3(PMePh2)2{NC(PMePh2)(p-C6H4Br}(8d),respectively.Thestructuresof8b−dhaveallbeenconfirmedbyX-raydiffractionstudies.Themolecularstructureof8cisshowninFigure3,andthoseof8band8daregiveninFiguresS2andComplex8aisdiamagneticandcanbecharacterizedbysolutionNMR.Consistentwiththesolid-statestructure,the31P{1H}NMRspectrumshowedtwosingletsignalsat−3.7and−37.2ppm.The1HNMRspectrumshowedtheCMesignalat2.84ppm(d,J=10.3Hz)andtwoPMesignalsat2.10(t,J=3.6Hz,6H,RePMe)and1.93(d,J=13.6Hz,3H,CPMe)ppm.Inthe13C{1H}NMRspectrum,theNC(Me)signalswereobservedat107.51(d,J=110.09Hz,C)and1.11(CMe)ppm.DuringtheprocessofcollectingNMRdataof8a,wenoticedthatcomplex8ainsolutioncanslowlyrevertbacktoReCl(PMePh)(6).Asindicatedby1HNMR,afterstoring323Figure3.Crystalstructureofcomplex8c.Hydrogenatomsandasolutionpreparedbydissolvingasolidsampleof8ainsolventmoleculesareomittedforclarity.Selectedbondlengths[Å]CD2Cl2for7h,ca.5%of8awasconvertedto6.After2days,andangles[°]:Re(1)−N(1)1.7819(18),N(1)−C(1)1.319(3),ca.25%of8awasconvertedto6.P(1)−C(1)1.779(2),95.70(6),C(1)−N(1)−Re(1)176.48(16),TheazavinylidenecomplexReCl3(PMePh2)2{NC-C(1)−N(1)−P(1)114.35(16).(PMePh2)Me}(8a)isinterestingasitrepresentsthefirstexampleofanazavinylidenecomplexwithaphosphine(PR3)substituent.Reportedazavinylidenecomplexesaremainly26,27S3.Thestructuralfeaturesofcomplexes8b−dderivedfromconfinedtothosewithH,alkyl,andarylsubstituents.Aarylnitrilecomplexesaresimilartothoseof8aderivedfromanfewrheniumazavinylidenecomplexeshavebeenreportedand11,19alkylnitrilecomplex,asindicatedbytheselectedstructuralweregeneratedbyalternativeroutes,forexample,18,28parametersshowninTable1.protonationofnitrilecomplexes,deprotonationofimido20,2930complexesandinsertionofnitriles.Table1.SelectedBondLengths(Å)andAngles(deg)ofTheunexpectedformationofphosphonium-substitutedComplexes7a,7c,and8a−dazavinylidenecomplex8afromthereactionofacetonitrilewithReCl3(PMePh2)3promotedustostudythereactionsofcomplexC−NRe−NRe−N−CC(1)−PReCl3(PMePh2)3witharylnitriles.TreatmentofRe-Cl3(PMePh2)3with2equivofNCPhinrefluxingtoluenefor8b1.314(3)1.779(2)176.17(17)1.787(2)ca.4hproducedtheazavinylidenecomplexRe-8c1.319(3)1.7819(18)176.48(16)1.779(2)Cl3(PMePh2)2{NC(PMePh2)Ph}(8b)(Scheme4).8d1.308(3)1.785(2)177.41(19)1.780(3)Underidenticalreactionconditions,thereactionsof8a1.302(5)1.789(3)179.74(10)1.781(3)ReCl3(PMePh2)3withp-NCC6H4Meandp-NCC6H4Br7a1.139(3)2.039(2)176.2(2)producedcomplexesReCl3(PMePh2)2{NC(PMePh2)(p-7c1.139(4)2.043(3)169.8(3)360https://dx.doi.org/10.1021/acs.organomet.0c00704Organometallics2021,40,358−369

3Organometallicspubs.acs.org/OrganometallicsArticleThesolid-statestructuresaresupportedbythesolutiongeneratedfromthereactionofReCl3(PMePh2)3withalargeNMRdata.Forexample,the31P{1H}NMRspectrumof8bexcessofMeCN.showedtwosingletsignalsat−1.9and−37.0ppm.TheReactionsofReCl3(NCPh)(PPh3)2withPPh3andPMe3.13C{1H}NMRspectrumshowedtheNCsignalat116.07Theaboveexperimentalobservationsindicatethatadditionofppm(d,J=111.5Hz).PMePh2tocoordinatednitrilesismorefavorablefornitrilesAsindicatedby1HNMR,azavinylidenecomplexeswithanelectron-withdrawinggroup.OnemightexpectthattheReCl3(PMePh2)2{NC(PMePh2)(p-C6H4R)}(R=Hbasicityofphosphinesmayalsoaffectthereactivity.Tostudy(8b),Me(8c),andBr(8d))insolutioncanundergopartialtheeffectofphosphineonthenucleophilicadditionreactionsdissociationofPMePh2toformnitrilecomplexesRe-togiveazavinylidenecomplexes,wehavestudiedthereactionsCl3(PMePh2)2(p-NCC6H4R)(R=H(7b),Me(7c),andBrofthereadilyavailablenitrilecomplexReCl3(PPh3)2(NCPh)(7d))(Scheme4).Thedegreeofthephosphinedissociationis(9)withPPh3andPMe3.dependentonthesubstituentsofthearylringoftheThecomplexReCl3(PPh3)2(NCPh)(9)wasfoundtobearylnitriles.Accordingto1HNMRintegrations,afterunreactivetowardPPh3.Theresultisnotsurprisingasithasdissolutionofsolidsamplesof8binCD2Cl2for7h,aboutbeenreportedthatthemonomericrhenium(III)complexes2%of8bwasconvertedto7b.Undersimilarconditions,aboutReCl3(PAr3)2(NCR)(R=MeandPh;Ar=Ph,p-tol,andm-11%of8cwasconvertedto7c,andlessthan1%of8dwastol)canbepreparedbythereactionsofReOCl3(PAr3)2withanexcessofthecorrespondingtriarylphosphinesandanconvertedto7d.Itappearsthatthephosphinesubstituentin14organonitrile.theazavinylidenecomplexesReCl3(PMePh2)2{NC-(PMePh2)(p-C6H4R)}ismoretightlyboundbythenitrileIncontrast,ReCl3(PPh3)2(NCPh)(9)reactedwithPMe3carboninthosecomplexesderivedfromanarylnitrilebearinginstantaneously.ThereactionofReCl3(PPh3)2(NCPh)withPMe3ina1:5molarratiogavetheazavinylidenecomplexanelectron-withdrawinggrouponthearylring.ThenitrilecomplexesReCl(PMePh)(p-NCCHR)(R=ReCl3(PMe3)2{NC(PMe3)Ph}(11),whichcanbe32264isolatedasapurplesolid(Scheme5).Thestructureof11H(7b),Me(7c),andBr(7d))havebeensynthesizedindependentlybythesubstitutionreactionsofRe-Cl(PMePh)(NCMe)(7a)withp-NCCHR(Scheme4).Scheme5.ReactionofReCl3(PPh3)3(NCPh)withPMe332264Thearylnitrilecomplexes(7b−d)havebeencharacterizedbyNMRandelementalanalysis.Thestructureofthecomplex7chasalsobeenconfirmedbyasingle-crystalX-raydiffractionstudy(seeTable1andFigureS1fordetail).ReactionsofReCl3(PMePh2)2(NCAr)andRe-Cl3(PMePh2)2(NCMe)withPMePh2.Itiswell-establishedthatcoordinatedorganonitrileligandcanbeattackedby5,31nucleophiles.ThusitisreasonabletoassumethatinthereactionsofReCl3(PMePh2)3withorganonitrilesazavinylidenecomplexes8wereformedbynucleophilicadditionreactionsoforganonitrilecomplexesReCl3(NCR)(PMePh2)2withfreephosphinePMePh2.Toconfirmthehypothesis,wehavestudiedthereactionsofReCl3(PMePh2)2{p-NCC6H4R)(R=H(7b),Me(7c),andBr(7d))withPMePh2.UponadditionofPMePh2toanorangesolutionofReCl3(PMePh2)2(p-NCC6H5)(7b)indichloromethane,thecolorchangedinstantlyfromorangetopurpleatroomtemperature.The31P{1H}NMRspectrumofthemixtureshowedtwosignalsatcanbereadilyassignedonthebasisoftheNMRdata.The−1.9and−37.0ppm,confirmingthatcomplex7bcanindeed31P{1H}NMRspectrumof11inCDClshowedtwosinglet22beattackedbyexternalphosphinePMePh2togeneratethesignalsat−8.4(CPMe)and−53.7(RePMe)ppm.The1H33azavinylidenecomplexReCl3(PMePh2)2{NC(PMePh2)-NMRspectrumshowedtwoPMe3signalsat2.04(d,J=13.3Ph}(8b).Underthesamereactioncondition,complexes7cHz,9H,CPMe3)and1.37(t,J=3.6Hz,18H,RePMe3)ppm.and7dwerealsofoundtorapidlyreactwithPMePh2togiveInthe13C{1H}NMRspectrum,theNC(Ph)signalwasthecorrespondingazavinylidenecomplexes(Scheme4).observedat111.94ppm(d,J=113.7Hz).SubstitutionreactionsofnitrilecomplexesLnM−NCRwithComplex11waspresumablyformedbynucleophilicphosphinesPR3′togivephosphinecomplexesLnM−PR3′areadditionofPMe3toReCl3(PPh3)2(NCPh)togiveazavinyli-32well-documentedreactions.Inprinciple,thereactionsofdenecomplex10,followedbysequentialsubstitutionoftwoReCl3(PMePh2)2(p-NCC6H4R)(R=H(8b),Me(8c),andBrPPh3ligandswithPMe3(Scheme5).Wehavetriedtodetect(8d))withPMePh2mayalsogivethesubstitutionproducttheintermediatesbyrunningthereactionwithalimitingReCl3(PMePh2)3.However,suchreactionswerenotobserved.amountofPMe3.When1equivofPMe3wasaddedtoaWehavealsostudiedthereactionofRe-suspensionofReCl3(PPh3)2(NCPh)intoluene,thesolidofCl3(PMePh2)2(NCMe)(7a)withPMePh2.ThereactionofReCl3(PPh3)2(NCPh)partiallydissolvedandreactedtogiveapurplesolutioncontainingtwo31PNMRactiveproducts.Onecomplex7awith1.1equivofPMePh2atroomtemperaturewasfoundtomainlygiveReCl3(PMePh2)3formedbyaligandisReCl3(PMe3)2{NC(PMe3)Ph}(11),whichshowed31P{1H}signalsat−7.5and−52.6ppm.Theotheronesubstationreaction.Theresultisconsistentwiththeobservationmentionedabovethattheazavinylidenecomplexdisplayedasingletat−6.5ppmandtwodoubletsat−22.2andReCl3(PMePh2)2{NC(PMePh2)Me}(8a)canonlybe−50.2ppmwithacouplingconstantof324Hz.TheNMR361https://dx.doi.org/10.1021/acs.organomet.0c00704Organometallics2021,40,358−369

4Organometallicspubs.acs.org/OrganometallicsArticledataareconsistentwiththestructureoftheazavinylidenecomplextrans-ReCl3(PPh3)(PMe3){NC(PMe3)Ph}(10′)(Scheme5).The31Psignalsat−6.5,−22.2,and−50.2ppmcanbeassignedtoCPMe3,RePPh3,andRePMe3,respectively.Inagreementwiththeformulation,theinter-mediatecanreactwithexcessofPMe3togive11.Attemptstoobtainapuresampleof10′wereunsuccessful.MagneticPropertiesofReCl3(PR3)2(L)(L=PR3andNCR′)andReCl3(PR3)2{NC(PR3)R′}.Itisnotedthatthed4phosphinecomplexesReCl(PR)andnitrilecomplexes333ReCl3(PR3)2(NCR′)haveatripletgroundstate,whiletheazavinylidenecomplexesReCl3(PR3)2{NC(PR3)R′}haveasingletgroundstate.Thepreferenceinthespinstateofthesecomplexesisunderstandableconsideringtheirelectronicstructures.AsshowninFigure4,theorbitalinteractionofaCd42vRe(III)fragmentReCl3L2withaσ-donorligandL′(e.g.,Figure5.CalculatedenergyprofilesforthesubstitutionreactionofReCl3(PMePh2)3(6)withNCMeandthesubsequentadditionreactionwithPMePh2.Therelativefreeenergiesandelectronicenergies(inparentheses)aregiveninkcal/mol.Figure4.SchematicorbitalinteractiondiagramsforReCl3L2L′andReCl3L2{NC(PR3)R′}derivedfromorbitalinteractionsofaC2vd4Re(III)fragmentReClLwithaσ-donorligandL′andtheligand32Figure6.CalculatedenergyprofilesforthesubstitutionreactionofNC(PR3)R′havingbothσandπfrontierorbitals,respectively.ReCl3(PMePh2)3withp-NCC6H4BrandthesubsequentadditionreactionwithPMePh2.Therelativefreeenergiesandelectronicphosphineornitrile)givessix-coordinatedcomplexesenergies(inparentheses)weregiveninkcal/mol.ReCl3L2L′.ThefourdelectronsintheseRe(III)complexesremaintooccupythethree“t2g”orbitalsleadingtoatripletelectronconfiguration.TheorbitalinteractionofaCd4thetripletparamagneticcomplexReCl(PMePh)(NCMe)2v322Re(III)fragmentReCl3L2withNC(PR3)R′givesazaviny-(7a)followingbyadditionofphosphinetogivethesingletlidenecomplexesReCl3L2{NC(PR3)R′}.SinceNdiamagneticazavinylideneReCl3(PMePh2)2{NC-C(PR3)R′containsbothσ-andπ-donors,azavinylidene(PMePh2)Me}(8a).SincetheadditionreactioninvolvesacomplexesReCl3L2{NC(PR3)R′}are18-electronspeciestriplet-to-singletstateconversion,wehavecalculatedthewithnounpairedelectrons,andhaveasingletgroundstate.energyprofilesforbothsingletandtripletstates.OurComputationalStudies.Theexperimentsdescribedcalculationsconfirmedthat6and7ahaveatripletgroundaboveshowthatphosphinescouldaddtocoordinatednitrilesstate,whileazavinylidenecomplex8ahasasingletgroundstatetogiveazavinylidenecomplexes,thefeasibilityofwhichis(Figure5).Thecalculatedstructuralparametersof7aand8adependentonphosphinesaswellasorganonitriles.ToverifyareingoodagreementwiththeexperimentalX-raycrystaltheproposedreactionmechanismandtohaveabetterstructuraldata(seeFigureS4fordetail).understandingoftheexperimentalobservations,wehaveAsshowninFigure5,thesubstitutionreactionofcalculatedtheenergyprofilesforthereactionsofRe-ReCl3(PMePh2)3(6)withNCMetogiveRe-Cl3(PMePh2)3(6)withNCMe(Figure5)andp-NCC6H4RCl3(PMePh2)2(NCMe)(7a)andPMePh2wasfoundtobe(R=H(FigureS6),Me(FigureS7),andBr(Figure6))andthermodynamicallyalmostneutralorslightlyendergonic(bythereactionsofReCl3(PPh3)2(NCPh)(9)withPMe3(Figure0.8kcal/mol).TheadditionofPMePh2to7atogivethe7a)andPPh3(Figure7b).ThecalculatedprofilesareingoodazavinylidenecomplexReCl3(PMePh2)2{NC(PMePh2)-agreementswiththeexperimentalobservations(seeSchemeMe}(8a)wasalsofoundtobealmostthermodynamicallyS1intheSupportingInformationfordetails).neutralorslightlyendergonic(by0.2kcal/mol).ThefavorableLetusfirstcommentonthemainfeaturesoftheenergytransitionstatefortheadditionreactionof7atogive8aisprofilesbyusingtheprofilecalculatedforthereactionofTS7a(t),whichcorrespondstoatripletstate.Triplet-to-singletReCl3(PMePh2)3(6)withNCMeasanexample(Figure5).stateconversionoccursafterthetransitionstateisreached.ThereactionwasproposedtoproceedbyinitialformationofTheadditionreactionhasabarrierof22.3kcal/mol,362https://dx.doi.org/10.1021/acs.organomet.0c00704Organometallics2021,40,358−369

5Organometallicspubs.acs.org/OrganometallicsArticleReCl3(PMePh2)2(p-NCC6H4R)(R=H,Me,andBr)(7b−d)withPMe2Phtogive6arethermodynamicallyunfavorablewhiletheadditionreactionstogiveazavinylidenes8arethermodynamicallyfavorableoralmostneutral,thereactionsofReCl3(PMePh2)2(p-NCC6H4R)(R=H,Me,andBr)(7b−d)withPMe2Phgivethecorrespondingazavinylidenecomplexes,ratherthanReCl3(PMePh2)3(6).WeobservedexperimentallythatReCl3(PPh3)2(NCPh)canreactwithPMe3togiveazavinylidenecomplex11viaintermediate10,butitdoesnotreactwithPPh3(Scheme5).ThecalculatedenergyprofilesforthereactionsofReCl3(PPh3)2(NCPh)(9)withPMe3(Figure7a)andPPh3(Figure7b)suggestthattheexperimentalobservationsarealsothermodynamicallycontrolledinorigin.AsshowninFigure7a,thereactionofPPMe3withReCl3(PPh3)2(NCPh)(9)togivetheazavinylidenecomplexReCl3(PPh3)2{NC(PMe3)Ph}(10)isathermodynamicallyfavoredprocess.AsshowninFigure7b,boththeadditionofPPh3toReCl3(PPh3)2(NCPh)(9)togivetheazavinylidenecomplexReCl3(PPh3)2{NC(PPh3)Ph}(13)andthesubstitutionreactionofReCl3(NCPh)(PPh3)2(9)withPPh3togiveReCl3(PPh3)3(14)arethermodynamicallyunfavorable.Thecomputationalstudiesrevealthatthethermodynamicsandthekineticsofnucleophilicadditionreactionarestronglyaffectedbyphosphines.Forexample,theadditionofPMe3toReCl3(PPh3)2(NCPh)(9)togivetheazavinylidenecomplexReCl3(PPh3)2{NC(PMe3)Ph}(10)wasfoundtobethermodynamicallyfavoredby4.3kcal/molwithabarrierof14.6kcal/mol,whiletheanalogousreactionwithPPh3isthermodynamicallyunfavoredby13.2kcal/molwithabarrierFigure7.Calculatedreactionprofileforthesubstitutionandadditionof26.8kcal/mol(Figure7).TheobservedphosphineeffectreactionsofReCl3(PPh3)2(NCPh)withPMe3(top,(a))andPPh3correlateswellwiththebasicityofphosphines,whileasteric(bottom,(b)).Therelativefreeenergiesandelectronicenergies(inparentheses)weregiveninkcal/mol.effectalsoplaysarole.Theadditionreactionisthermodynami-callymorefavorableandkineticallymorefeasiblewhenthephosphineismoreelectron-donatingandlessstericallyconfirmingthatthenucleophilicadditionreactioniskineticallydemanding.Theeffectofnitrilesonthermodynamicsandfeasible.thekineticsoftheadditionreactionwasalsonoted.Kinetically,TheenergyprofilescanhelpustounderstandexperimentaltheadditionofphosphinetoalkylnitrileMeCN(Figure5)isobservations.TheprofileinFigure5providesanexplanationlessfavorablethanthattoarylnitriles(Figure6).ontheexperimentalobservationsassociatedwiththeThermodynamically,additionofphosphinetoalkylnitrilesubstitutionreactionofNCMewithReCl3(PMe2Ph)3(6)MeCNisslightlylessfavorablethantoPhCN.Foradditionandthesubsequentreactionof7awithPMePh2.Sincethereactionsofarylnitriles,theonewithanelectron-withdrawingreactionsof6withMeCNtogive7aand8aareslightlygroupismorefavorable.thermodynamicallyunfavorablewithasimilarendothermicity,ThesubstitutionreactionsofReCl2(PR3)3(NCR′)withalargeamountofnitrilesareneededtoshiftthereactionphosphinesarealsoaffectedbyphosphinesandnitriles.Fortowardproducts,andundersuchconditions,thereactionexample,thesubstitutionreactionofReCl3(PPh3)2(NCPh)wouldgenerateamixtureoftheazavinylidenecomplex(9)withPMe3togiveReCl3(PPh3)3(PMe3)(12)andNCPhReCl3(PMePh2)2{NC(PMePh2)Me}(8a)andnitrilewasfoundtobethermodynamicallyfavoredby1.4kcal/mol,complex7a.Asthereactionof7awithPMePh2togive6iswhiletheanalogousreactionwithPPh3isthermodynamicallythermodynamicallymorefavorablethanthattogive8a,unfavoredby15.3kcal/mol(Figure7).Thephosphineeffectcomplex7areactedwithPMePh2togive6,ratherthan8a.canberelatedtothestericandelectronicpropertiesoftheTheenergyprofilesforreactionsofReCl3(PMePh2)3(6)phosphineligands.Thereactionisthermodynamicallymorewithp-NCC6H4R(R=H(FigureS6),Me(FigureS7),andBrfavorablewhenaphosphineisstericallylessdemandingand(Figure6))provideanexplanationontheexperimentalelectronicallymoredonating.AstericeffectmightbethemajorobservationsassociatedwiththereactionsofReCl3(PMePh2)3factorcausingthesubstitutionreactionof(6)witharylnitrilesp-NCC6H4R(R=H,Me,andBr)andtheReCl3(PPh3)2(NCPh)(9)withPPh3togiveReCl3(PPh3)3reactionsofReCl3(PMePh2)2(p-NCC6H4R)(R=H,Me,andtobesignificantlymoreendothermic.TheeffectofnitrilesonBr)(7b−d)withPMe2Ph.SincethereactionsofRe-thereactionsarealsonotable.Forexample,thesubstitutionCl3(PMePh2)3(6)witharylnitrilesArCNtogivenitrilereactionofReCl3(PMePh2)2(NCMe)(7a)withPMe2Phtocomplexes7andazavinylidenecomplexes8arethermody-giveReCl3(PMePh2)3(6)andMeCNisslightlyfavoredby0.8namicallyfavorable,thereactionsofReCl3(PMePh2)3(6)withkcal/mol(Figure5),whilethereactionofarylnitrilearylnitrilescanproceedwithouttheneedofusinganexcesscomplexesReCl3(PMePh2)2(NCAr)withPMe2Phisthermo-amountofarylnitriles.Sincesubstitutionreactionsofdynamicallyunfavoredbyca.4kcal/mol(Figures6,S6,and363https://dx.doi.org/10.1021/acs.organomet.0c00704Organometallics2021,40,358−369

6Organometallicspubs.acs.org/OrganometallicsArticle1HNMR).Thedarkgreencrystalsof8acanbepickedupbyhandforS7).Theobservationsseemcloselyrelatedtothedifferenceinthebindingabilityofthealkylandarylnitriles.WenoticedthatX-raydiffractionstudyandelementalanalysisofthecrystalmixture.CharacterizationDataofReCl(PMePh)(NCMe)(7a).1HNMRthecalculatedRe−NbondinReCl3(PMePh2)2(NCMe)is3222.020Å,whilethatinReCl3(PMePh2)2(NCPh)is2.001Å,(400MHz,CDCl3)δ57.26(s,3H,NCMe),14.38(d,J=7.5Hz,8H,suggestingthatNCPhisabetterligandforReCl(PMePh)Ph),9.35(t,J=7.5Hz,4H,Ph),9.13(t,J=7.5Hz,8H,Ph),0.82(s,3226H,PMePh).13C{1H}NMR(101MHz,CDCl)δ215.19(s,thanMeCN.Thedifferenceinthebindingabilityofthealkyl2333NCMe),156.89(s,NCMe),135.20(s,Ph),133.11(s,Ph),126.53(s,andarylnitrilesisalsoreflectedbyNBOanalysis,showingPh),80.06(s,Ph).Anal.CalcdforC28H29Cl3NP2Re:C,45.82;H,thattheMayer−MullikenbondordercalculatedfortheRe−N3.98;N,1.91.Found:C,45.61;H,4.13;N,2.13orC,45.95;H,4.15;bondinReCl3(PMePh2)2(NCMe)is0.4025,whiletheindexN,2.12.calculatedfortheRe−NbondinReCl3(PMePh2)2(NCPh)isCharacterizationDataofReCl3{NC(PMePh2)Me)}(PMePh2)2(8a).31P{1H}NMR(162MHz,CDCl)δ−3.67(s),−37.19(s).1H0.4274.NCPhisprobablyabetterligandthanNCMebecause22NCPhisabetterπ-acceptingligand,resultinginastrongerNMR(400MHz,CD2Cl2)δ7.79−6.93(m,30H,Ph),2.84(d,J=back-donationinteractionfromthemetalcentertotheligand.10.3Hz,3H,NC−Me),2.10(t,J=3.6Hz,6H,PMePh2),1.93(d,J=13.6Hz,3H,[PMePh]+).13C{1H}NMR(101MHz,CDCl)δ222143.31−122.72(m,Ph),107.51(d,J=110.09Hz,ReN=C),12.51(t,J=16.0Hz,PMePh),8.84(d,J=60.6Hz,[PMePh]+),1.11(s,■CONCLUSIONS22WehavedemonstratedthatacoordinatedorganonitrileligandsNC−Me).Anal.CalcdforC41H42Cl3NP3Re:C,52.71;H,4.53;N,1.50.Found:C,52.28;H,4.43;N,1.54.incertainrhenium(III)complexescanbeattackedbyReCl3(PMePh2)2{NC(PMePh2)Ph}(8b).Toasuspensionofphosphinestogiverheniumphosphonium-azavinylideneReCl3(PMePh2)3(200mg,0.224mmol)intoluene(8.0mL)wascomplexes.TheazavinylidenecomplexesRe-injectedbenzonitrile(0.12mL,1.12mmol).ThereactionmixturewasCl3(PMePh2)2{NC(PMePh2)Ar}(Ar=Ph,p-C6H4Me,refluxedforca.4htogiveadarkpurplesolution.Thereactionp-C6H4Br,andMe)canbeobtainedbythereactionsofmixturewascooleddowntoroomtemperature.ThesolventoftheReCl3(PMePh2)3withorganonitrilesNCAr,orthereactionsofreactionmixturewasremovedinvacuotogiveadarkpurpleresidue.ReCl3(PMePh2)3(NCAr)withPMePh2.ThecomplexRe-Theresiduewasredissolvedindichloromethane(2.0mL)togiveaCl3(PMe3)2{NC(PMe3)R}wasproducedinthereactiondarkpurplesolution.AdarkpurplesolidwasprecipitatedoutafterofReCl3(PPh3)2(NCPh)withPMe3.Computationalstudyaddingdiethylether(10.0mL)tothedarkpurplesolution.Thissolidshowsthatthereactionsarethermodynamicallycontrolled.wasrecrystallizedwithdichloromethane(1.0mL)anddiethylether(5.0mL)togivedarkpurplecrystalsof8b.Yield:72.4mg,32.4%.Bothexperimentalandcomputationalstudiessuggestthat31P{1H}NMR(162MHz,CDCl)δ−1.89(s),−37.01(s).1Hnucleophilicadditionofphosphinestocoordinatednitrilesis22NMR(400MHz,CD2Cl2)δ7.77−6.76(m,35H,Ph),2.03(m,9H,morefavorablefornitrileswithanelectron-withdrawinggroup+131PMePh2and[PMePh2]).C{H}NMR(100MHz,CD2Cl2)δandformorebasicphosphines.134.92−123.30(m,Ph),116.07(d,J=111.5Hz,ReN=C),12.27(t,J=16.5Hz,PMePh),11.17(d,J=60.6Hz,[PMePh]+).Anal.22■EXPERIMENTALSECTIONCalcdforC46H44Cl3NP3Re:C,55.45;H,4.45;N,1.41.Found:C,55.60;H,4.37;N,1.38.GeneralConsiderations.AllmanipulationswerecarriedoutReCl3(PMePh2)2(NCPh)(7b).ToasolutionofRe-underanitrogenatmosphereusingstandardSchlenktechniquesCl3(PMePh2)2(NCMe)(7a;500mg,0.583mmol)intoluene(10.0unlessotherwisestated.Literaturemethodswereusedforthe3435mL)wasinjectedbenzonitrile(0.30mL,2.91mmol).ThereactionpreparationofReCl3(PMePh2)3andReCl3(PPh3)2(NCPh).mixturewasrefluxedforca.6h.ThereactionmixturewascooledDiethylether,n-hexane,andtetrahydrofuran(THF)weredistilleddowntoroomtemperature,andthenconcentratedbyreducingitsundernitrogenfromsodiumbenzophenone.Dichloromethanevolumebyapproximatelyhalfinvacuotogiveanorangeprecipitate.(DCM)andacetonitrile(MeCN)weredistilledundernitrogenTheorangeprecipitatewascollectedbyfiltration,washedwithdiethylfromcalciumhydride.AllotherreagentswerepurchasedfromSigma-11131ether(3×10mL),andair-dried.Yield:400mg,58.0%.HNMRAldrichChemicalCo.andusedasreceived.H,C{H},and311(400MHz,CDCl3)δ14.69(d,J=7.5Hz,8H,Ph),11.39(t,J=7.7P{H}NMRspectrawerecollectedonaBrukerARX-4001131Hz,2H,p-NCC6H5),9.26(t,J=7.5Hz,4H,Ph),9.08(t,J=7.5Hz,spectrometer(400MHz).HandC{H}chemicalshiftsare3118H,Ph),4.39(t,J=7.7Hz,1H,p-NCC6H5),4.11(d,J=7.6Hz,2H,relativetoTMS,andP{H}chemicalshiftsarerelativeto85%p-NCC6H5),0.45(s,6H,PMePh2).H3PO4.FormationofReCl(PMePh){NC(PMePh)Me)}(8a)ReCl3(PMePh2)2{NC(PMePh2)(p-C6H4Me)}(8c).Toa3222yellowsuspensionofReCl(PMePh)(250mg,0.280mmol)inandReCl3(PMePh2)2(NCMe)(7a)fromtheReactionof323ReCl3(PMePh2)3withAcetonitrile.Ayellowsuspensionoftoluene(8.0mL)wasadded4-methylbenzonitrile(65.6mg,0.560ReCl3(PMePh2)3(500mg,0.600mmol)inacetonitrile(8.0mL)mmol).Thereactionmixturewasrefluxedforca.6htogiveadarkwasrefluxedforca.6htogiveadarkgreensolution.Thereactionpurplesolution.Thereactionmixturewascooleddowntoroommixturewascooleddowntoroomtemperature.Thevolumeofthetemperature.Thesolventofthereactionmixturewasremovedinreactionmixturewasreducedtohalfinvacuotogenerateanorangevacuotogiveadarkpurpleresidue.Theresiduewasredissolvedinprecipitate.Afteradditionofdiethylether(10.0mL)tothedichloromethane(2.0mL)togiveadarkpurplesolution.Adarkconcentratedreactionmixture,theorangesolidwascollectedbypurplesolidwasprecipitatedoutbyaddingdiethylether(10.0mL)tofiltration,washedwithdiethylether(3×10.0mL),anddriedtogivethedarkpurplesolution.ThissolidwasrecrystallizedwithpuresamplesofReCl3(NCMe)(PMePh2)2(7a,yield:192mg,dichloromethane(1.5mL)anddiethylether(7.0mL)togivedarkpurplecrystalsof8c.Yield:71.9mg,25.4%.31P{1H}NMR(16243.5%).ThedarkgreenfiltratewascollectedandconcentratedbyMHz,CDCl)δ−0.53(s),−35.51(s).1HNMR(400MHz,reducingitsvolumebyapproximatelyhalf.Diethylether(10.0mL)22waslayeredontopoftheconcentrateddarkgreenfiltratetogiveaCD2Cl2)δ7.62−6.72(m,34H,Ph),2.49(s,3H,p-NCC6H4Me),2.03crystallinedarkgreensolidmixedwithanorangesolid.Thissolid(t,J=3.3Hz,6H,RePMePh2),1.98(d,J=13.9Hz,3H,CPMePh2).13C{1H}NMR(101MHz,CDCl)δ135.13−123.41(m,Ph),mixturewasrecrystallizedwithdichloromethane(1.0mL)anddiethyl22ether(5.0mL)togive76.2mg(13.6%)ofacrystallinesolid116.44(d,J=112.11Hz,ReN=C)19.63(s,p-NCC6H4Me),12.29composedofmainlydarkgreencrystalsofReCl3(PMePh2)2{N(t,J=16.5Hz,RePMePh2),11.11(d,J=61.61Hz,CPMePh2).Anal.C(PMePh2)Me)}(8a)andasmallamountofyellowmicrocrystalsofCalcdforC41H42Cl3NP3Re:C,52.71;H,4.53;N,1.50.Found:C,ReCl3(NCMe)(PMePh2)2(7a)(inca.3:1molarratioasindicatedby52.28;H,4.43;N,1.54.364https://dx.doi.org/10.1021/acs.organomet.0c00704Organometallics2021,40,358−369

7Organometallicspubs.acs.org/OrganometallicsArticleReCl(PMePh)(p-NCCHMe)(7c).ToasolutionofRe-(t,J=3.6Hz,18H,RePMe).13C{1H}NMR(100MHz,CDCl):δ3264322Cl3(PMePh2)2(NCMe)(7a;500mg,0.583mmol)intoluene(10.0127.52(s,Ph),126.27(s,Ph),124.88(s,Ph),111.94(d,J=113.7mL)wasadded4-methylbenzonitrile(341mg,2.91mmol).TheHz,ReN=C),12.84(d,J=55.7Hz,CPMe3),11.93(t,J=14.9Hz,reactionmixturewasrefluxedforca.8h.ThereactionmixturewasRePMe3).Anal.CalcdforC16H32Cl3NP3Re:C,30.80;H,5.17;N,cooleddowntoroomtemperatureandthenconcentratedbyreducing2.25.Found:C,30.56;H,5.29;N,2.23orC,30.14;H,5.27;N,2.14.itsvolumebyabouthalfinvacuotogiveanorangeprecipitate.TheX-rayCrystallography.Thecrystalsof8a,7a·NCMe,8b,8c·orangeprecipitatewascollectedbyfiltration,washedwithdiethyl0.5CH2Cl2·0.5C4H10O,7c·CH2Cl2,and8d·0.15CH2Cl2·0.85C4H10Oether(3×10.0mL),andair-dried.Yield:137mg,29.0%.1HNMRweregrownbyappropriatesolventdiffusionofmethylenechloride(400MHz,CD2Cl2)δ14.73(d,J=7.6Hz,8H,Ph),11.41(d,J=7.7andTHFunderaninertatmosphereofnitrogenatroomtemperature.Hz,2H,p-NCC6H4Me),9.26(t,J=7.4Hz,4H,Ph),9.15−9.03(m,AllspecimensweremountedinairwithMiTeGenLoops.Intensity8H,Ph),8.93(s,3H,p-NCC6H4Me),3.39(d,J=8.2Hz,2H,p-131datawerecollectedonaRigaku-OxfordDiffractionSuperNovaAtlasNCC6H4Me),0.70(s,6H,PMePh2).C{H}NMR(101MHz,CCDdiffractometerat100K.DiffractiondatawereprocessedusingCD2Cl2)δ233.32(s,Re−NC),168.92(s,Ph),134.87(s,Ph),theCrysAlisProsoftware(version1.171.35.19).Empiricalabsorption133.66(s,Ph),126.67(s,Ph),119.75(s,Ph),72.70(s,Ph),10.61(s,correctionswereperformedusingsphericalharmonics,implementedp-NCC6H4Me).Anal.CalcdforC34H33Cl3NP2Re·H2O:C,49.31;H,4.26;N,1.69.Found:C,49.75;H,4.23;N,1.65.intheSCALE3ABSPACKscalingalgorithmintheCrysAlisProReCl3(PMePh2)2{NC(PMePh2)(p-C6H4Br)}(8d).Toayel-softwaresuite.StructuresolutionandrefinementforallcompoundslowsuspensionofReCl3(PMePh2)3(200mg,0.224mmol)intoluenewereperformedusingtheOlex2softwarepackage(whichembedded(8.0mL)wasadded4-bromobenzonitrile(81.5mg,0.448mmol).SHELXL).Allofthestructuresweresolvedbydirectmethods,Themixturewasrefluxedforca.6htogiveadarkpurplesolution.expandedbydifferenceFouriersynthesesandrefinedbyfullmatrixleast-squaresonF2.Allthenon-hydrogenatomswererefinedThereactionmixturewascooleddowntoroomtemperature.Thesolventofthereactionmixturewasremovedinvacuotogiveadarkanisotropicallywitharidingmodelforthehydrogenatoms.Furtherpurpleresidue.Theresiduewasredissolvedindichloromethane(2.0crystallographicdetailsaresummarizedinTableS1.mL)togiveadarkpurplesolution.AdarkpurplesolidwasThemolecularstructuresofthesecomplexesareshowninFiguresprecipitatedoutbyaddingdiethylether(10mL)tothedarkpurpleS1−S6.Crystallographicdatahavebeendepositedwiththesolution.Thissolidwasrecrystallizedwithdichloromethane(1.0mL)CambridgeCrystallographicDataCentre.CCDC1994609(8a),anddiethylether(5mL)togivedarkpurplecrystals,whichwere1994614(7a·NCMe),1994617(8b),1994618(8c·0.5CH2Cl2·collectedbyfiltration,driedundervacuum.Yield:107mg,44.5%.0.5C4H10O),1994619(7c·CH2Cl2)and1994627(8d·0.15CH2Cl2·31P{1H}NMR(162MHz,CDCl)δ−1.71(s),−37.41(s).1H220.85C4H10O)containcrystallographicdataforthispaper.ThesedataNMR(400MHz,CD2Cl2)δ7.80−6.69(m,34H,Ph),2.21−1.93(m,canbeobtainedfreeofchargefromTheCambridgeCrystallographic9H,RePMePhandCPMePh).13C{1H}NMR(100MHz,CDCl)δ2222DataCentreviawww.ccdc.cam.ac.uk/data_request/cif.134.90−117.18(m,Ph),114.78(d,J=113.12Hz,ReN=C)12.17ComputationalDetail.DFTcalculationswereperformedusing(t,J=16.7Hz,RePMePh2),10.98(d,J=61.61Hz,CPMePh2).Anal.theGaussian09D.01package.36AllthestructureswereoptimizedCalcdforC46H43BrCl3NP3Re·Et2O:C,52.52;H,4.65;N,1.22.usingtheM06functional37withthebasissetLanl2dzforRe38and6-Found:C,52.58;H,4.33;N,1.33.3931G*formaingroupatoms.Polarizationfunctions(ζf=0.869)ReCl3(PMePh2)2(p-NCC6H4Br)(7d).ToasolutionofRe-40wereaddedforRe.Acorrectionof−2.6kcal/molwasmadeforCl3(PMePh2)2(NCMe)(7a;500mg,0.583mmol)intoluene(10.0two-to-one(or2.6kcal/molforone-to-two)transformations.mL)wasadded4-bromobenzonitrile(530mg,2.91mmol).TheFrequencycalculationswereperformedtoverifytheoptimizedreactionmixturewasrefluxedforca.8handthencooleddowntoroomtemperature.Thereactionmixturewasconcentratedbystructuresaslocalminimaortransitionstatesandtoobtainrelativereducingitsvolumeinvacuotohalftogiveanorangeprecipitate.Gibbsfreeenergies(withintheharmonicapproximation)at298.15K.Theorangeprecipitatewasfilteredoutunderair.ItwaswashedwithTransitionstatestructureswereconfirmedtoconnectappropriatediethylether(3×10.0mL)andair-dried.Yield:178mg,34.9%.1Hreactantsorproductsbyintrinsicreactioncoordinate(IRC)41NMR(400MHz,CDCl3)δ14.65(d,J=7.4Hz,8H,Ph),11.64(d,Jcalculations.SolventeffectsofMeCN(Figure5)ortoluene=8.0Hz,2H,p-NCC6H4Br),9.29(t,J=7.5Hz,4H,Ph),9.07(t,J=(Figures6and7)accordingtotheexperimentalconditionwere427.6Hz,8H,Ph),4.13(d,J=8.0Hz,2H,p-NCC6H4Br),0.13(s,6H,consideredusingtheSMDmodeattheM06/6-311++G**levelPMePh).13C{1H}NMR(100MHz,CDCl)δ251.16(s,Re−N23withLanl2dzpluspolarizationfunctionsforRe.C),150.72(s,Ph),135.43(s,Ph),133.32(s,Ph),130.55(s,Ph),126.32(s,Ph),65.35(s,Ph).CalcdforC33H30BrCl3NP2Re:C,45.30;■H,3.46;N,1.60.Found:C,45.10;H,3.65;N,1.54orC,45.02;H,ASSOCIATEDCONTENT3.65;N,1.57.*sıSupportingInformationReCl3(PMe3)2{NC(PMe3)Ph}(11).ToasuspensionofTheSupportingInformationisavailablefreeofchargeatReCl3(PPh3)2(NCPh)(9,100mg,0.109mmol)intoluene(8.0https://pubs.acs.org/doi/10.1021/acs.organomet.0c00704.mL)wasinjectedtrimethylphosphine(0.10mL,0.109mmol).TheyellowsolidofReCl3(NCPh)(PPh3)2partiallydissolvedandtheNMRspectra;crystallographicdataofthecomplexes7a,reactionmixtureimmediatelychangedcolorfrompale-yellowtodark7c,8a−d;energyprofilesofthecomputationalstudypurple.Thereactionmixturewasstirredat60°Cfor30mintogivea(PDF)purplesolutionwithasmallamountyellowsolid(presumablyunreactedstartingmaterial).ThereactionmixturewascooleddownCartesiancoordinates(XYZ)toroomtemperatureandfilteredtogiveadarkpurplesolution.Thedarkpurplesolutionwasdriedinvacuotogiveadarkpurpleresidue.Thedarkpurpleresiduewasredissolvedindichloromethane(1.0mL)AccessionCodestogiveadarkpurplesolution.Diethylether(8.0mL)wasaddedtoCCDC1994609,1994614,1994617−1994619,and1994627thedarkpurplesolutiontoprecipitateadarkpurplesolid.Thedarkcontainthesupplementarycrystallographicdataforthispaper.purplesolidwasseparatedbyfiltration.AcrystallinesolidwasThesedatacanbeobtainedfreeofchargeviawww.ccdc.ca-obtainedbyrecrystallizationwithdichloromethane(1.0mL)and311m.ac.uk/data_request/cif,orbyemailingdata_request@ccdc.diethylether(5.0mL).Yield:24.9mg,36.7%.P{H}NMR(162MHz,CDCl)δ−8.42(s),−53.68(s).1HNMR(400MHz,cam.ac.uk,orbycontactingTheCambridgeCrystallographic22CD2Cl2):δ7.35(t,J=7.7Hz,2H,Ph),7.04(d,J=7.9Hz,2H,Ph),DataCentre,12UnionRoad,CambridgeCB21EZ,UK;fax:6.97(t,J=7.4Hz,1H,Ph),2.04(d,J=13.3Hz,9H,CPMe3),1.37+441223336033.365https://dx.doi.org/10.1021/acs.organomet.0c00704Organometallics2021,40,358−369

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