Terminal tungsten pnictide complex formation through pnictaethynolate decarbonylation

Tungsten(iv) tetrakis(2,6-diisopropylphenoxide) (1) has been demonstrated to be a competent platform for decarbonylative formation of anionic terminal pnictide complexes upon treatment with pnictaethynolate anions: cyanate, 2-phosphaethynolate, and 2-arsaethynolate. These transformations constitute...

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Bibliographic Details
Published in:Chemical communications (Cambridge, England) England), 2017, Vol.53 (77), p.10731-10733
Main Authors: Joost, Maximilian, Transue, Wesley J, Cummins, Christopher C
Format: Article
Language:English
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Summary:Tungsten(iv) tetrakis(2,6-diisopropylphenoxide) (1) has been demonstrated to be a competent platform for decarbonylative formation of anionic terminal pnictide complexes upon treatment with pnictaethynolate anions: cyanate, 2-phosphaethynolate, and 2-arsaethynolate. These transformations constitute the first examples of terminal phosphide and arsenide complex formation at a transition metal center from OCP and OCAs , respectively. The phosphide and arsenide complexes are also the first to be isolated in a tetragonal, all-oxygen ligand environment. The scalar NMR coupling constants between tungsten-183 and nitrogen-15 or phosphorus-31 have been measured and contextualized using natural bond orbital (NBO) methods in terms of s orbital character in the σ bonding orbital and pnictide lone pair.
ISSN:1359-7345
1364-548X
DOI:10.1039/c7cc06841g