ALKENE ISOMERIZATION CATALYZED WITH PLATINUM HYDRIDE COMPLEXES

被引：5

作者：

PERMIN, AB

PETROSYAN, VS

机构：

来源：

APPLIED ORGANOMETALLIC CHEMISTRY | 1990年 / 4卷 / 04期

关键词：

alkene; catalysis; Isomerization; mechanism; phosphine; platinum hydrides; tin trihalide complexes of platinum;

D O I：

10.1002/aoc.590040405

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

The mechanism of but‐1‐ene, pent‐1‐ene and 3‐methylbut‐1‐ene isomerization catalysed with trans‐[PtH(SnX3)L2] (I, L = PPh3, PMePh2, PEt3, PPr3; X = Cl, Br) have been studied. Stoichiometric reactions of I with the alkenes proceed even at −90°C giving cis‐[Pt(alkyI‐1) (SnX3) L2] (II). The equilibrium amounts of II are dependent on the nature of the phosphines, halogens and alkenes. The isomerization rates, determined at +20°C, change in parallel with the relative stabilities of II as a function of phosphine (PMePh2 > PPh3 > PAlk3) and halogen (Br > Cl), and decrease with methyl substitution at γ‐ and δ‐ carbons of the alkenes. 2‐Substituted alk‐1‐enes undergo no isomerization in the reactions under investigation. When L is PPh3 or PMePh2, the main platinum‐containing species in the course of the isomerization are trans‐[Pt(alkyl‐1) (SnX3)L2], appearing as a result of cis‐trans isomerization of II. The conversion of I, L = PAlk3 into related trans‐alkyl complexes, and oxidation of I, proceed more slowly than the isomerization of alkenes. The ratio of cis‐ to trans‐alk‐2‐enes is dependent on the size of L and is a maximum for L = PPh3. Copyright © 1990 John Wiley & Sons Ltd.

引用

页码：329 / 333

页数：5

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