INTERCONVERSION OF ETA(1)-PROPARGYL, ETA(1)-ALLENYL, AND ETA(3)-PROPARGYL ALLENYL LIGANDS ON PLATINUM - SYNTHESIS, STRUCTURE, AND REACTIVITY OF [(PH3P)2PT(ETA(3)-CH2CCPH)]O3SCF3

被引:91
作者
BLOSSER, PW [1 ]
SCHIMPFF, DG [1 ]
GALLUCCI, JC [1 ]
WOJCICKI, A [1 ]
机构
[1] OHIO STATE UNIV,DEPT CHEM,COLUMBUS,OH 43210
关键词
D O I
10.1021/om00030a001
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The eta3-propargyl/allenyl complex [(Ph3-P)2Pt(eta3-CH2CCPh)]+ (4), formed by reaction of trans-(PPh3)2PtBr(eta1-CH2C=CPh) with AgO3SCF3 or (Ph3-P)2Pt(eta2-PhC=CCH2OMe) with BF3.OEt2, reacts with Br-to yield 9:1 cis-/trans-(Ph3P)2PtBr(eta1-CH2C=CPh), with excess PMe3 to give [(Me3P)3Pt(eta1-C(Ph)=C=CH2)]+, and with CO to afford 1:1 [trans-(Ph3P)2Pt(CO)(eta1-CH2C=CPh)]+/[trans- (Ph3P)2Pt(CO) (eta1-C(Ph)=C=CH2)]+. With Et2NH, ROH (R = Me, Et), and CH(CO2Me)2-, 4 undergoes nucleophilic addition to the central C atom with transfer of hydrogen to the CPh atom of eta3-CH2CCPh to produce eta3-allyl complexes as single syn or anti isomers.
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页码:1993 / 1995
页数:3
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