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Pentamethylcyclopentadienyl Halfsandwich Complexes of Vanadium and Tantalum with Amido‐, Imido‐ Nitrido‐ and Azido Ligands
Author(s) -
Herberhold Max,
Dietel AnnaMaria,
Goller Achim,
Milius Wolfgang
Publication year - 2003
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200390148
Subject(s) - chemistry , trimethylsilyl , ligand (biochemistry) , medicinal chemistry , amide , trimethylsilyl azide , vanadium , stereochemistry , azide , tantalum , organic chemistry , receptor , biochemistry
Lithium bis(trimethylsilyl)amide, LiN(SiMe 3 ) 2 , reacts with Cp*V(O)Cl 2 and Cp*TaCl 4 to give trimethylsilylimido complexes such as [Cp*V(NSiMe 3 )(μ‐NSiMe 3 )] 2 ( 7 ) and Cp*Ta(Cl)(NSiMe 3 )[N(SiMe 3 ) 2 ] ( 19 ), respectively. Substitution of the chloro ligand in 19 by anionic groups leads to complexes with 3 different N‐containing ligands, Cp*Ta(X)(NSiMe 3 )[N(SiMe 3 ) 2 ] (X = N 3 ( 20 ) or NPEt 3 ( 21 )). Complex 7 is air‐ and moisture‐sensitive, and several derivatives containing oxo and trimethylsiloxy ligands have been identified. Trimethylsilyl azide, Me 3 Si‐N 3 , is able to replace the oxygen‐containing ligands for azido ligands. The two complete series of bis(azido)‐bridged complexes, [Cp*VCl n (N 3 ) 2‐n (μ‐N 3 )] 2 (n = 2, 1, 0) and [Cp*TaCl n (N 3 ) 3‐n (μ‐N 3 )] 2 (n = 3, 2, 1, 0), are accessible from the reactions of Cp*VCl 3 and Cp*TaCl 4 , respectively, with trimethylsilyl azide. A bis(nitrido)‐bridged azido‐vanadium complex, [Cp*V(N 3 )(μ‐N)] 2 ( 18 ), has also been obtained and structurally characterized.