Terminal tungsten pnictide complex formation through pnictaethynolate decarbonylation

Abstract

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.