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The imidovanadium(III) complexes [tBuN=VCp(PR3)2], [tBuN=VCp{P(OR)3}2] and [tBuN= VCp(CO)2] have been prepared starting from tBuN=VCpCl2by reductive dehalogenation with magnesium. The reaction of [tBuN=VCp(PMe3)2] (2a) with carbon monoxide, alkynes, alkenes, tert-butylphosphaalkyne, nitriles, ketones and carbon disulfide furnished the complexes [tBuN=VCp(PMe3) (L)], while the vanadium(V) compound tBuN=VCp(O2C2Ph2) is formed with benzil. All vanadium(III) complexes obtained are diamagnetic (d2, low-spin configuration) and have been characterized by spectroscopic methods (MS; 1H, 13C, 31P, 51V NMR).

The reaction of [tBuN=VCp(PMe3)2] (1) with S8, Se, Te or I2have been studied. Via this pathway dinuclear diamagnetic tert-butylimidovanadium(IV) complexes are formed: [(µ-E)(µ- NtBu)2V2Cp2] (E=S, Se, Te), [(µ-?1-E2)(µ-NtBu)2V2Cp2] {E=Se (3), Te}, [(µ-NtBu)2V2Cp2I2]. In addition the vanadium(V) complexes [tBuN=VCp (S5)] (9a) and tBuN=VCpI2could be isolated. The synthesis of tBuN=VCpF2is also described. All compounds obtained have been characterized by spectroscopic methods (MS; 1H, 13C, 51V NMR), 3 and 9b by single crystal X-ray diffraction analysis.