Reactivity of ammonium and iminium tetraphenylborates towards Pd(0)-complexes:: selective allyl or proton transfer to Pd(0).: Evidence of formation of the species [HPd(dppe)2][BPh4]

被引：4

作者：

Aresta, M ^{[1
]}

Quaranta, E ^{[1
]}

机构：

[1] CNR, Dipartimento Chim, ICCOM, I-70126 Bari, Italy

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2002年 / 662卷 / 1-2期

关键词：

Pd-allyl complexes; Pd-hydrido complexes; allyl transfer; proton transfer; alkylammonium tetraphenylborates; iminium tetraphenylborates;

D O I：

10.1016/S0022-328X(02)01897-1

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reactivity of ammonium- and iminium-BPh4 Salts, [CH2=CHCH2NH3]BPh4, [(CH2=CHCH2)HN=CMe2]BPh4 and [(PhCH2)HN=CMe2]BPh4, towards Pd(0)-complexes, [Pd(dppe)(dba)] and [Pd(dppe)(2)] (dppe = 1,2-bis(diphenylphosphino)ethane; dba = dibenzylideneacetone), has been investigated. Allyl-ammonium and -iminium tetraphenylborates [CH2=CHCH2NH3]BPh4 and [(CH2=CHCH2)HN=CMe2]BPh4 react with [Pd(dppe)(dba)] to afford, under mild conditions (293 K), [(eta(3)-C3H5)Pd(dppe)][BPh4], through selective oxidative transfer of allyl group from the ammonium or iminium cation to the Pd center. [(PhCH2)HN CMe2]BPh4 reacts with [Pd(dppe)(2)] to afford [H-Pd(dppe)(2)][BPh4], that, under the reaction conditions, has poor stability as it undergoes hydride transfer to the iminium ion present in the reaction medium, affording [Pd(dppe)(2)][BPh4](2). (C) 2002 Elsevier Science B.V. All rights reserved.

引用

页码：112 / 119

页数：8

共 61 条

[1] Gated migration for enantioselective synthesis of palladium allyls using a "PdHBr" synthon [J].