Coordinatively Unsaturated W(IV)−Bis(pyridine) Complexes, a Reactive Source of W(IV)

Addition of 2 equiv of a σ-donor ligand (L = pyridine, 4-picoline, or quinoline) to complexes of the type [W(NPh)(η4-arene)(o-(Me3SiN)2C6H4)] (arene = CH3CH2C6H5 (3), CH3CH2CH2C6H5 (4)) gave the W(IV)L2 compounds,
[W(NPh)(o-(Me3SiN)2C6H4)(C5H5N)2] (5), [W(NPh)(o-(Me3SiN)2C6H4)(p−C6H7N)2] (6), and [W(NPh)(o-(Me3SiN)2C6H4)(C9H7N)2] (7). Synthesis of compounds 5 and 6 by Na° reduction of [W(NPh)(o-(Me3SiN)2C6H4)Cl2]
in the presence of 3 equiv of L (L = 5, pyridine or 6, 4-picoline) is also presented. Compounds 5, 6, and 7
display hindered rotation of the donor ligands about the W−N bonds, resulting from a steric interaction with the
Me3Si groups of the diamide ligand. The coordinative unsaturation of 5 and 6 has also been explored. Compounds
5 and 6 readily react with either CO and PMe3 to generated the six coordinate complexes [W(NPh)(o-(Me3SiN)2C6H4)(C5H5N)2(CO)] (8a), [W(NPh)(o-(Me3SiN)2C6H4)(C6H7N)2(CO)] (8b), [W(NPh)(o-(Me3SiN)2C6H4)(C5H5N)(PMe3)2] (10a), and [W(NPh)(o-(Me3SiN)2C6H4)(C6H7N)(PMe3)2] (10b), respectively.