资源描述：
《butylphosphinito ) pyridine Pincer Complexes - Swisher, Grubbs - Unknown - Unknown》由会员上传分享，免费在线阅读，更多相关内容在学术论文-天天文库。
SupportingInformationSynthesisandCharacterizationof3,5-Bis(di-tert-butylphosphinito)pyridinePincerComplexesNicholasA.SwisherandRobertH.GrubbsArnoldandMabelBeckmanLaboratoriesofChemicalSynthesis,CaliforniaInstituteofTechnology,Pasadena,California91125,UnitedStatesTableofContents:1.NMRSpectraS2-S252.InfraredSpectraS26-S273.CyclicVoltammetryDataS28-S294.X-RayCrystallographicInformationS30-S315.ReferencesS32S1
1NuclearMagneticResonanceSpectra554654229.5.5.5.7.7.7.1.0.9888777710N(tBu)2POOP(tBu)2070.0.8.3611314131211109876543210-1-2f1(ppm)FigureS1.1HNMR(400MHz,C6D6)spectrumof3,5-bis(di-tert-butylphosphinito)pyridine,1.S2
2776766285.0.0.0.3.3.3.3.1.1888777511N(tBu)2POOP(tBu)2021.0.3.9610314131211109876543210-1-2f1(ppm)FigureS2.1HNMR(400MHz,CD2Cl2)spectrumof3,5-bis(di-tert-butylphosphinito)pyridine,1.S3
35.6751N(tBu)2POOP(tBu)21901801701601501401301201101009080706050403020100-10-20-30-40f1(ppm)FigureS3.31P{1H}NMR(162MHz,C6D6)spectrumof3,5-bis(di-tert-butylphosphinito)pyridine,1.S4
49.80.81.71.695147386644.34.24.14.5.2.0.85533111557611111113322N(tBu)2POOP(tBu)22102001901801701601501401301201101009080706050403020100-10f1(ppm)FigureS4.13C{1H}NMR(101MHz,C6D6)of3,5-bis(di-tert-butylphosphinito)pyridine,1.S5
592607.6.6.1.9.887700B(C6F5)3Ntt(Bu)2POOP(Bu)2050.0.0.0621314131211109876543210-1f1(ppm)FigureS5.1HNMR(400MHz,C6D6)spectrumofN-tris(pentafluorophenyl)borane-3,5-bis(di-tert-butylphosphinito)pyridine,2.S6
64.6071B(C6F5)3Ntt(Bu)2POOP(Bu)21901801701601501401301201101009080706050403020100-10-20-30-40f1(ppm)FigureS6.31P{1H}NMR(162MHz,C6D6)spectrumofN-tris(pentafluorophenyl)borane-3,5-bis(di-tert-butylphosphinito)pyridine,2.S7
78950838.4.6.7.8.9.0.0155523335556661111111-------B(C6F5)3N(tBu)2POOP(tBu)23020100-10-20-30-40-50-60-70-80-90-100-110-120-130-140-150-160-170-180-190-200f1(ppm)FigureS7.19F{1H}NMR(376MHz,C6D6)spectrumofN-tris(pentafluorophenyl)borane-3,5-bis(di-tert-butylphosphinito)pyridine,2.S8
8230.50863890621249148.88.789.17.81.09.56.02.81.38.08.87.71.61.51.0.8.8.655444333322222265661111111111111113322B(C6F5)3N(tBu)2POOP(tBu)22102001901801701601501401301201101009080706050403020100-10f1(ppm)FigureS8.13C{1H}NMR(101MHz,C6D6)ofN-tris(pentafluorophenyl)borane-3,5-bis(di-tert-butylphosphinito)pyridine,2.S9
95253188.8.3.3.3.3.8.07511100NOO(tBu)2PRhP(tBu)2CO01.0.261314131211109876543210-1-2f1(ppm)FigureS9.1HNMR(400MHz,CD2Cl2)spectrumof(PyPOCOP)Rh(CO),3.Contaminationbysmallamountsofsiliconegreaseandpentaneispresent.S10
1015.8.8092122NOO(tBu)2PRhP(tBu)2CO2902702502302101901701501301109070503010-10-30-50f1(ppm)FigureS10.31P{1H}NMR(162MHz,CD2Cl2)spectrumof(PyPOCOP)Rh(CO),3.S11
11344455912589482847093153951.6.5.4.0.9.8.0.0.9.1.9.8.0.9.911.1.0.0.0000099665433655.3.1.8.5.3.9.9.4.4.40000996665552224433300009988822221111111111155555444433222NOO(tBu)2PRhP(tBu)2CO2102001901801701601501401301201101009080706050403020100-10f1(ppm)FigureS11.13C{1H}NMR(101MHz,CD2Cl2)of(PyPOCOP)Rh(CO),3.S12
12224208.7.3.3.3.3.0751110B(C6F5)3NOO(tBu)2PRhP(tBu)2CO09.0.761314131211109876543210-1-2f1(ppm)FigureS12.1HNMR(400MHz,CD2Cl2)spectrumof(BCF-PyPOCOP)Rh(CO),4.Contaminationbyasmallamountofsiliconegreaseispresent.S13
1374.7.8872222B(C6F5)3NOO(tBu)2PRhP(tBu)2CO2902702502302101901701501301109070503010-10-30-50f1(ppm)FigureS13.31P{1H}NMR(162MHz,CD2Cl2)spectrumof(BCF-PyPOCOP)Rh(CO),4.S14
141051116.1.7.7.8.7.7.7288844435556661111111-------B(C6F5)3NOO(tBu)2PRhP(tBu)2CO3020100-10-20-30-40-50-60-70-80-90-100-110-120-130-140-150-160-170-180-190-200f1(ppm)FigureS14.19F{1H}NMR(376MHz,CD2Cl2)spectrumof(BCF-PyPOCOP)Rh(CO),4.S15
158.39.73.32.23.14.06.92.5032.56.154208147078045285398666659.17.4186.39.58.65.03.3.1.8.5.3.6.5.5.5.3.3.2.7.27996666644433222244333000488824.11111111111111111555554443222211B(C6F5)3NOO(tBu)2PRhP(tBu)2CO2102001901801701601501401301201101009080706050403020100-10f1(ppm)FigureS15.13C{1H}NMR(101MHz,CD2Cl2)of(BCF-PyPOCOP)Rh(CO),4.S16
16863192.0.1.2.2.1.4871110B(C6F5)3NOO(tBu)2PNiP(tBu)2Br02.0.062314131211109876543210-1f1(ppm)FigureS16.1HNMR(400MHz,C6D6)spectrumof(BCF-PyPOCOP)NiBr,5.Contaminationbywaterispresent.S17
171.3602B(C6F5)3NOO(tBu)2PNiP(tBu)2Br2902702502302101901701501301109070503010-10-30-50f1(ppm)FigureS17.31P{1H}NMR(162MHz,C6D6)spectrumof(BCF-PyPOCOP)NiBr,5.S18
18522089.6.3.5.5.4.0751110B(C6F5)3NOO(tBu)2PNiP(tBu)2Br02.0.362314131211109876543210-1-2f1(ppm)FigureS18.1HNMR(400MHz,CD2Cl2)spectrumof(BCF-PyPOCOP)NiBr,5.Contaminationbyasmallamountofsiliconegreaseispresent.S19
190.9402B(C6F5)3NOOtt(Bu)2PNiP(Bu)2Br2402302202102001901801701601501401301201101009080706050403020100-10-20-30-40f1(ppm)FigureS19.31P{1H}NMR(162MHz,CD2Cl2)spectrumof(BCF-PyPOCOP)NiBr,5.S20
20683982480.0.6.7.7.9.0.0.0.1255523333355566666111111111---------B(C6F5)3NOO(tBu)2PNiP(tBu)2Br3020100-10-20-30-40-50-60-70-80-90-100-110-120-130-140-150-160-170-180-190-200f1(ppm)FigureS20.19F{1H}NMR(376MHz,CD2Cl2)spectrumof(BCF-PyPOCOP)NiBr,5.S21
217778916635479672081470592074.86.76.66.42.22.12.49.07.61.19.98.78.58.46.26.16.73.3.1.8.5.3.1.0.0.2.1.186665554443333333244333111888.111111111111111111555554442221B(C6F5)3NOOtt(Bu)2PNiP(Bu)2Br2102001901801701601501401301201101009080706050403020100-10f1(ppm)FigureS21.13C{1H}NMR(101MHz,CD2Cl2)of(BCF-PyPOCOP)NiBr,5.Contaminationbyasmallamountofsiliconegreaseispresent.S22
22322088.7.3.5.5.4.0751110NOOtt(Bu)2PNiP(Bu)2Br03.0.961314131211109876543210-1-2f1(ppm)FigureS22.1HNMR(400MHz,CD2Cl2)spectrumof(PyPOCOP)NiBr,6.Contaminationbyasmallamountofsiliconegreaseispresent.S23
234.8591NOO(tBu)2PNiP(tBu)2Br2902702502302101901701501301109070503010-10-30-50f1(ppm)FigureS23.31P{1H}NMR(162MHz,CD2Cl2)spectrumof(PyPOCOP)NiBr,6.S24
242.83.73.68.48.29.0681470814296.76668886.3.1.8.5.3.3.3.2.3.2.27666333244333000888.11111111555554442221NOO(tBu)2PNiP(tBu)2Br2102001901801701601501401301201101009080706050403020100-10f1(ppm)FigureS24.13C{1H}NMR(101MHz,CD2Cl2)of(PyPOCOP)NiBr,6.Contaminationbyasmallamountofsiliconegreaseispresent.S25
25InfraredSpectraB(C6F5)3NOO(tBu)2PRhP(tBu)2COFigureS25.IRspectrum(ATR-IR,thinfilmTHF)of(BCF-PyPOCOP)Rh(CO),4.S26
26NOO(tBu)2PRhP(tBu)2COFigureS26.IRspectrum(ATR-IR,thinfilmTHF)of(PyPOCOP)Rh(CO),3.S27
27CyclicVoltammetry25B(C6F5)320N15OO(tBu)2PNiP(tBu)2BrA)10�5Current(01.11.21.31.41.51.61.71.81.9-5-10Potential(V)vs.FeCp*2FigureS27.Cyclicvoltammogramofcomplex5inCH2Cl2with0.1M(n-Bu4N)(PF6)electrolyte.E1/2=1.68VandEox=1.74Vvs.decamethylferrocene.S28
281412NOO10(tBu)2PNiP(tBu)2Br86Current(µA)42011.11.21.31.41.51.61.71.81.9-2Potentialvs.FeCp*2FigureS28.Cyclicvoltammogramofcomplex6inCH2Cl2with0.1M(n-Bu4N)(PF6)electrolyte.Eox=1.749Vvs.decamethylferrocene.S29
29X-RayStructureDeterminationCompound5(BCF-PyPOCOP)NiBrLow-temperaturediffractiondata(f-andw-scans)werecollectedonaBrukerAXSD8VENTUREKAPPAdiffractometercoupledtoaPHOTON100CMOSdetectorwithMoKaradiation(l=0.71073Å)fromanIμSmicro-sourceforthestructureofcompound5.ThestructurewassolvedbydirectmethodsusingSHELXSandrefinedagainstF2onalldatabyfull-matrixleastsquareswithSHELXL-2016usingestablishedrefinementtechniques.1-3Allnon-hydrogenatomswererefinedanisotropically.Allhydrogenatomswereincludedintothemodelatgeometricallycalculatedpositionsandrefinedusingaridingmodel.Theisotropicdisplacementparametersofallhydrogenatomswerefixedto1.2timestheUvalueoftheatomstheyarelinkedto(1.5timesformethylgroups).Compound5crystallizesinthemonoclinicspacegroupP21/nwithonemoleculeintheasymmetricunit.S30
30EmpiricalformulaC39H38BBrF15NNiO2P2Formulaweight1049.07Temperature100(2)KWavelength0.71073ÅCrystalsystemMonoclinicSpacegroupP21/nUnitcelldimensionsa=18.331(2)Åa=90°.b=12.0823(15)Åb=99.077(5)°.c=19.875(3)Åg=90°.Volume4346.9(9)Å3Z4Density(calculated)1.603Mg/m3Absorptioncoefficient1.539mm-1F(000)2112Crystalsize0.450x0.450x0.400mm3Thetarangefordatacollection2.250to36.417°.Indexranges-28<=h<=30,-20<=k<=20,-33<=l<=33Reflectionscollected151341Independentreflections21162[R(int)=0.0554]Completenesstotheta=25.242°99.9%AbsorptioncorrectionSemi-empiricalfromequivalentsMax.andmin.transmission0.7471and0.6178RefinementmethodFull-matrixleast-squaresonF2Data/restraints/parameters21162/0/571Goodness-of-fitonF21.025FinalRindices[I>2sigma(I)]R1=0.0357,wR2=0.0693Rindices(alldata)R1=0.0611,wR2=0.0765Extinctioncoefficientn/aLargestdiff.peakandhole0.918and-0.964e.Å-3TableS1.Crystaldataandstructurerefinementforcomplex5.S31
31References1.Sheldrick,G.M.PhaseAnnealinginSHELX-90:DirectMethodsforLargerStructures.Acta.Cryst.1990,A46,467-473.2.Sheldrick,G.M.AShortHistoryofSHELX.Acta.Cryst.2008,A64,112-122.3.Müller,P.PracticalSuggestionsforBetterCrystalStructures.CrystallographyReviews2009,15,57-83.S32
