Jump to main content
Jump to site search

Issue 28, 2019
Previous Article Next Article

Phosphaisonitrile umpolung – synthesis and reactivity of chloro aminophosphino carbynes

Author affiliations

Abstract

Sequential treatment of [W([triple bond, length as m-dash]CBr)(CO)2(Tp*)] (Tp* = hydrotris(dimethylpyrazolyl)borate) with nBuLi and Cl2PNiPr2 provides the aminochlorophosphinocarbyne [W([triple bond, length as m-dash]CPClNiPr2)(CO)2(Tp*)]. The chloro substituent undergoes subsitution with RLi (R = Me, Et, Ph) to afford [W([triple bond, length as m-dash]CPRNiPr2)(CO)2(Tp*)] and with [W([triple bond, length as m-dash]CLi)(CO)2(Tp*)] to give the aminobis(alkylidynyl)phosphine [iPr2NP{C[triple bond, length as m-dash]W(CO)2(Tp*)}2]. Treatment with Li[BHEt3] gives the primary aminophosphine [W([triple bond, length as m-dash]CPHNiPr2)(CO)2(Tp*)], formed in a mixture with the ethyl derivative [W([triple bond, length as m-dash]CPEtNiPr2)(CO)2(Tp*)]. Although they could not be isolated, spectroscopic data indicated that halide abstraction with Al2Cl6 forms the phosphaisonitrile salt [W(CPNiPr2)(CO)2(Tp*)][AlCl4], which displays electrophilic character at phosphorus, e.g., in the reaction with diphenylacetylene to furnish the phosphirenium salt [W{CP(C2Ph2)NiPr2}(CO)2(Tp*)][AlCl4]. Finally, the reaction with LiNPh2 gives the mixed diaminophosphinocarbyne, [W{[triple bond, length as m-dash]CP(NiPr2)(NPh2)}(CO)2(Tp*)].

Graphical abstract: Phosphaisonitrile umpolung – synthesis and reactivity of chloro aminophosphino carbynes

Back to tab navigation

Supplementary files

Article information


Submitted
02 May 2019
Accepted
04 Jun 2019
First published
04 Jun 2019

Dalton Trans., 2019,48, 10628-10641
Article type
Paper

Phosphaisonitrile umpolung – synthesis and reactivity of chloro aminophosphino carbynes

A. L. Colebatch, B. J. Frogley and A. F. Hill, Dalton Trans., 2019, 48, 10628
DOI: 10.1039/C9DT01838G

Social activity

Search articles by author

Spotlight

Advertisements