Bis(organoimido)-complexes of tungsten(IV): the crystal and molecular structures of tetrachlorobis(t-butylamine)bis(t-butylimido)bis(µ-p-tolylimido)-ditungsten(VI) and tetrachlorobis(µ-phenylimido)-bis(t-butylamine) bis(t-butylimido)ditungsten(VI)

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Abstract
The tungsten(VI) organoimido complexes [{WCl4(NR)}2](R = Ph, C6H4Me-p, Pri, or Me) were treated with the silylamines Me3SiNHR″(R″= Ph, But, Pri, or Et) to form the dimeric complexes [{WCl2(NR)(NR″)(NH2R″)}2], containing terminal and bridging organoimido ligands, cis-oriented chloro ligands, and co-ordinated amine. [{WCl2(NPh)(NBut)(NH2But)}2] was also obtained from the reaction of [{WCl4(NPh)}2] with NH2But. Spectral studies suggest that these complexes arise from two cis-oriented organoimido groups by an inter-ligand proton-transfer process which proceeds regardless of the size of the group R. The structure of [{WCl2(NC6H4Me-p)(NBut)(NH2But)}2] was determined by X-ray crystallography and shown to have distorted edge-shared bioctahedral geometry with terminal t-butylimido groups and bridging unsymmetrical arylimido groups and with the longer W–N bridge bonds trans to the terminal t-butylimido group. The t-butylamine ligands are involved in intramolecular N–H Cl bridging within the dimeric unit, which explains some striking features found in the 1H n.m.r. spectrum. Full details are also given of the crystal structure of [{WCl2(NPh)(NBut)(NH2But)}2].

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