双（亚烷基）膦重排为磷酰基化合物。

Rearrangement of bis(alkylidynyl)phosphines to phospha-acyls.

作者信息

Colebatch Annie L, Han Yong-Shen, Hill Anthony F, Sharma Manab, Shang Rong, Ward Jas S

机构信息

Research School of Chemistry, Australian National University, Canberra, Australian Capital Territory, ACT 2601, Australia.

出版信息

Chem Commun (Camb). 2017 Feb 7;53(11):1832-1835. doi: 10.1039/c6cc09764b. Epub 2017 Jan 23.

DOI:10.1039/c6cc09764b

PMID:28111645

Abstract

A range of bis(alkylidynyl)phosphines RP{C[triple bond, length as m-dash]M(CO)(Tp*)} (M = Mo, W; R = Cl, Ph, Cy; Tp* = hydrotris(dimethylpyrazolyl)borate) are obtained from the reactions of [M([triple bond, length as m-dash]CLi)(CO)(Tp*)] with ClPR or alternatively via the palladium(0)-mediated reactions of [W([triple bond, length as m-dash]CBr)(CO)(Tp*)] with RPH (R = Py, Cy). The complexes RP{C[triple bond, length as m-dash]W(CO)(Tp*)} rearrange slowly (R = Cl) or on heating (R = Ph) to afford the isomeric phospha-acyls [W(μ:η-C;η-C,P-CCPR)(CO)(Tp*)].

摘要

一系列双（亚烷基）膦RP{C[三键，长度为m破折号]M(CO)(Tp*)}（M = Mo，W；R = Cl，Ph，Cy；Tp* = 氢三（二甲基吡唑基）硼酸酯）可通过[M([三键，长度为m破折号]CLi)(CO)(Tp*)]与ClPR的反应制得，或者通过钯(0)介导的[W([三键，长度为m破折号]CBr)(CO)(Tp*)]与RPH（R = Py，Cy）的反应制得。配合物RP{C[三键，长度为m破折号]W(CO)(Tp*)}会缓慢重排（R = Cl）或加热时重排（R = Ph），生成异构体磷酰基[W(μ:η-C;η-C,P-CCPR)(CO)(Tp*)]。