Issue 41, 2018

Synthesis and reactivity of selenium functionalised allylidynes and propargylidynes

Abstract

The reactions of the trimethylsilylpropargylidyne [W([triple bond, length as m-dash]CC[triple bond, length as m-dash]CSiMe3)(CO)2(Tp*)] (1: Tp* = hydrotris(dimethylpyrazolyl)borate) towards selenium centred reagents when treated with tetrabutylammonium fluoride (TBAF) were explored in order to prepare alkynylselenolato propargylidynes, e.g., [W([triple bond, length as m-dash]CC[triple bond, length as m-dash]CSePh)(CO)2(Tp*)]. Treating 1 with TBAF and PhSeSePh resulted in E and Z isomers of the vinylcarbyne (allylidyne) complex [W{[triple bond, length as m-dash]CC(SePh)[double bond, length as m-dash]CHSePh}(CO)2(Tp*)] in addition to traces of the trisubstituted derivative [W{[triple bond, length as m-dash]CC(SePh)[double bond, length as m-dash]C(SePh)2}(CO)2(Tp*)]. Reactions with PhSeCl resulted in the isolation of bimetallic bis-substituted allylidyne complex [(Tp*)(CO)2W[triple bond, length as m-dash]CC(SePh)[double bond, length as m-dash]C(SePh)C[triple bond, length as m-dash]CC[triple bond, length as m-dash]W(CO)2(CO)2(Tp*)] as well as the desired selenolatopropargylidyne [W([triple bond, length as m-dash]CC[triple bond, length as m-dash]CSePh)(CO)2(Tp*)].

Graphical abstract: Synthesis and reactivity of selenium functionalised allylidynes and propargylidynes

Supplementary files

Article information

Article type
Paper
Submitted
09 Jun 2018
Accepted
19 Sep 2018
First published
19 Sep 2018

Dalton Trans., 2018,47, 14621-14629

Synthesis and reactivity of selenium functionalised allylidynes and propargylidynes

A. F. Hill, R. A. Manzano and J. S. Ward, Dalton Trans., 2018, 47, 14621 DOI: 10.1039/C8DT02370K

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