AN ETA(2) TRANSITION-STATE FOR THE INSERTION OF M(PR3)2 FRAGMENTS (M = PD OR PT) INTO THE PHOSPHORUS CARBON BONDS OF PENTACARBONYL(PHOSPHIRANE)TUNGSTEN COMPLEXES

被引：29

作者：

CARMICHAEL, D ^{[1
]}

HITCHCOCK, PB ^{[1
]}

NIXON, JF ^{[1
]}

MATHEY, F ^{[1
]}

RICARD, L ^{[1
]}

机构：

[1] ECOLE POLYTECH,DCPH,CNRS,URA 1499,F-91128 PALAISEAU,FRANCE

来源：

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1993年 / 12期

关键词：

D O I：

10.1039/dt9930001811

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reaction of (E)- and (Z)-[W(CO)5(PPhCHPhCHPh)] complexes with [M(PR3)2(C2H4)] [M = Pd, (PR3)2 = dppe (PhPCH2CH2PPh2); M = Pt, PR3 = PPh3] has been studied and the following products [which result from insertion of the M(PR3)2 fragment into the phosphirane ring] have been fully characterised by NMR spectroscopy: (2R*,3S*,4S*)-(+/-)-, (2R*,3R*,4R*)-(+/-)- and (2R*,3S*,4R*)-(+/-)-[(dppe)Pd(CHPhCHPhPPh)W(CO)5]; (2S*,3S*,4S*)-(+/-)-, (2S*3R*4R*)-(+/-)- and (2S*,3S*,4R*)-(+/-)-[(Ph3P)2Pt(CHPhCHPhPPh)W(CO)5]; and trans-(2S*,3S*,4R*)-(+/-)-[(Ph3P)(OC)Pt-(CHPhCHPhPPh)W(CO)5]. The crystal and molecular structures of (Z)-[W(CO)5(PPhCHPhCHPh)], (2R*,3S*,4R*)-(+/-)- and (2R*,3S*,4S*)-(+/-)-[(dppe)Pd(CHPhCHPhPPh)W(CO)5] have been determined. The configurations of the products are interpreted in terms of a transition state in which a P-C bond is eta2-co-ordinated to the M (PR3)2 fragment.

引用

页码：1811 / 1822

页数：12

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