Vanadium Nitride Linear Chain Polymers and Monomers. Synthesis and Structures of (V(Mu-N)Cl2(py)2)2) Infinity and V(N)Cl2(quin)2

摘要

A series of vanadium(V) nitrido complexes of formula V(V(N)C12 L2)n has been prepared by net loss of chlorotrimethylsilane from the vanadium(V) trimethylsilylimido trichloride, CL3-NSiMe3 triple bond, on reaction with substituted pyridines or an amine. For L = py or 4-Mepy, insoluble nitride-bridged linear chain polymers are produced. An X-ray structure of V(mu-N)Cl2(py)2) infinity reveals distorted octahedral vanadium centers joined by alternating short (1.571 (7) A) and long (2.729(7) A) V-N bonds. In contrast, for L = 4-Etpy, 4-t-Bupy, or quinuclidine, soluble monomeric terminal nitride complexes are formed. The X-ray structure of V(N)Cl2(quin)2 indicates that this compound also possesses a monomeric five-coordinate structure in the solid state with a short (1.568 (19) A) terminal metal nitride bond. The stability of the nitride bridge is discussed in light of the differences in structure and solubility in this group of compounds and in terms of the observed interactions involving the ancillary ligands in the solid-state structure of V(mu-N)Cl2(py)2 infinity. Keywords: Chlorine, Synthesis chemistry, Molecular structure. Reprints. (aw)