113860-39-2Relevant academic research and scientific papers
Generation and trapping of transient cis-(η1-phosphinidene)(η 1-carbene)tetracarbonyltungsten complexes
Le Floch, Pascal,Huy, Ngoc Hoa Tran,Mathey, Fran?ois
, p. 1293 - 1296 (2008/10/08)
The reaction of n-butyl- or phenyllithium with (3,4-dimethyl-1-phenylphosphole)pentacarbonyltungsten followed by O-alkylation with [Et3O]BF4 gives the corresponding cis-(phosphole)(ethoxycarbene)W(CO)4 complexes. The [4 + 2] cycloaddition of the phosphole dienic system of these complexes with dimethyl acetylenedicarboxylate then affords the corresponding cis-(7-phosphanorbornadiene)(ethoxycarbene)W(CO)4 complexes. These 7-phosphanorbornadiene complexes can serve as precursors of transient cis-(phenylphosphinidene)(ethoxycarbene)W(CO)4 complexes under mild conditions. These transient species selectively react at phosphorus with alcohols and amines to give the corresponding cis- [PhP(H)A](ethoxycarbene)-W(CO)4 complexes (A = OR, NHR). When the amino group is sufficiently nucleophilic, intramolecular exchange takes place between the amino group at phosphorus and the ethoxy group of the carbene. No satisfactory trapping of the phosphinidene is observed with diphenylacetylene.
