Reaction of [2-(SiH3)C6H4]2SiH2 with Ni(Et2PCH2CH2PEt2)(PEt3)2: characterization of eta2-(Si-H)Ni and NiIV-H complexes

Wanzhi Chen; Shigeru Shimada; Masato Tanaka; Yuka Kobayashi; Kazuhiko Saigo

doi:10.1021/ja039244k

Reaction of [2-(SiH3)C6H4]2SiH2 with Ni(Et2PCH2CH2PEt2)(PEt3)2: characterization of eta2-(Si-H)Ni and NiIV-H complexes

J Am Chem Soc. 2004 Jul 7;126(26):8072-3. doi: 10.1021/ja039244k.

Authors

Wanzhi Chen¹, Shigeru Shimada, Masato Tanaka, Yuka Kobayashi, Kazuhiko Saigo

Affiliation

¹ National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan.

PMID: 15225021
DOI: 10.1021/ja039244k

Abstract

The reaction of (2-SiH3C6H4)2SiH2 with Ni(Et2PCH2CH2PEt2)(PEt3)2 afforded a new silylnickel complex, which, in the solid state, was determined to be a bis(silyl)eta2-(Si-H)nickel complex, the first example of eta2-(Si-H)nickel complex by single-crystal X-ray analysis. Variable-temperature NMR spectroscopy revealed fluxional behavior of the complex in solution; at room temperature, exchange of five hydrogens (two SiH2 and one hydrogen bound to nickel) was observed, while at -80 degrees C the exchange of hydrogens appeared frozen to adopt a tris(silyl)(hydrido)nickel(IV) structure, which was confirmed by theoretical calculation. The latter complex is the first example of hydridonickel(IV) complex.