Issue 8, 1977
From the journal:

Journal of the Chemical Society, Dalton Transactions

Unsaturated σ-hydrocarbyl transition-metal complexes. Part 2. Synthesis and reactions of vinylplatinum complexes and a comparison with analogous fluorovinyl and alkynyl complexes

Christine J. Cardin,   David J. Cardin  and  Michael F. Lappert  

Abstract

Alkenyl (CH[double bond, length as m-dash]CH2 or CF[double bond, length as m-dash]CF2) or alkynyl (C[triple bond, length half m-dash]CPh) derivatives of trimethyltin are shown to be superior to lithium or magnesium reagents for the synthesis of corresponding mono-organoplatinum(II) species by metathesis (L = SnMe3R +cis-[PtCl2L2]→trans-[PtRClL2]+ SnMe3Cl tertiary phosphine). The reactivity order for SnMe3R is R = C[triple bond, length half m-dash]CPh > CF[double bond, length as m-dash]CF2 > CH[double bond, length as m-dash]CH2. This order is also found for oxidative addition of SnMe3R to Pt0 to give cis-[PtRL2(SnMe3)]. When the latter complex (R = CH[double bond, length as m-dash]CH2) reacts with X2 or MeX further oxidative addition occurs exclusively at the platinum centre. Aromatic isonitriles (R′NC)co-ordinate to the platinum and give insertion products trans-[Pt{C(CH[double bond, length as m-dash]CH2)= NR′}ClL2] on heating or carbene complexes with NBunH2. The alkynyl trans-[Pt(C[triple bond, length half m-dash]CPh)ClL2] also forms 1 :1 adducts with R′NC and carbene complexes therefrom, but no insertion products. Spectroscopic data for the new complexes are presented.

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Article information

DOI
https://doi.org/10.1039/DT9770000767
Article type
Paper

J. Chem. Soc., Dalton Trans., 1977, 767-779

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Unsaturated σ-hydrocarbyl transition-metal complexes. Part 2. Synthesis and reactions of vinylplatinum complexes and a comparison with analogous fluorovinyl and alkynyl complexes

C. J. Cardin, D. J. Cardin and M. F. Lappert, J. Chem. Soc., Dalton Trans., 1977, 767 DOI: 10.1039/DT9770000767

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