HYDRIDE TO CARBENE MIGRATION AT PLATINUM(II) - SYNTHESIS AND X-RAY STRUCTURE OF CIS-((PPH3)2PT[C(H)SCH2CH2S])BF4

被引：23

作者：

MICHELIN, RA

BERTANI, R

MOZZON, M

BOMBIERI, G

BENETOLLO, F

DASILVA, MDCG

POMBEIRO, AJL

机构：

[1] UNIV PADUA,FAC INGN,CNR,CTR STUDIO CHIM & TECNOL COMPOSTI MET ORGAN ELEMENTI TRANSIZ,I-35131 PADUA,ITALY

[2] UNIV MILAN,IST CHIM FARMACEUT,I-20131 MILAN,ITALY

[3] CNR,IST CHIM & TECNOL RADIOELEMENTI,I-35100 PADUA,ITALY

[4] INST SUPER TECN,CTR QUIM ESTRUCT,P-1096 LISBON,PORTUGAL

来源：

ORGANOMETALLICS | 1993年 / 12卷 / 06期

关键词：

D O I：

10.1021/om00030a056

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The hydrido-dithiocarbene complex trans-[(PPh3)2PtH(CSCH2CH2S)]BF4 (1) undergoes thermal rearrangement in CH3CN by hydride to carbene migration to form the complex cis-{(PPh3)2Pt[C(H)SCH2CH2S]}-BF4 (2), whose molecular structure has been determined by a single-crystal X-ray analysis (monoclinic, P2(1)/n; a = 16.255 (3) angstrom, b = 20.423 (3) angstrom, c = 11.406 (2) angstrom, beta = 94.42 (4)-degrees, V = 3773(1) angstrom3, Z = 4, R = 0.047, R(w) = 0.054 for 4447 measured reflections with I > 3sigma(I)). The rearrangement of 1 to 2 proceeds also with Cl- ions. In this latter reaction the neutral complex trans-[(PPh3)2PtCl[C(H)SCH2CH2S] (3) could be isolated in the solid state, but it isomerizes in solution by intramolecular displacement of Cl- by one sulfur atom of the dithiolane ring to give cis-{(PPh3)2Pt[C(H)SCH2CH2S]}Cl (2'), which is structurally similar to 2.

引用

页码：2372 / 2376

页数：5

共 37 条

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