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Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV
Published on: December 29, 2016
Synthesis and reactivity of selenium functionalised allylidynes and propargylidynes
Anthony F Hill1, Richard A Manzano, Jas S Ward
1Research School of Chemistry, Australian National University, Acton, Canberra, A.C.T., Australia. a.hill@anu.edu.au.
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*)].
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