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Title: Dialkyl bis(bis(trimthylsilyl)amido) Group 4A metal complexes. Preparation of bridging carbene complexes by. gamma. elimination of alkane. Crystal structure of )ZrCHSi(Me)/sub 2/NSiMe/sub 3/(N(SiMe/sub 3/)/sub 2/))/sub 2/

Journal Article · · Organometallics; (United States)
DOI:https://doi.org/10.1021/om00073a005· OSTI ID:6909334

The dialkyls of zirconium of the type R/sub 2/Zr(N(SiMe/sub 3/)/sub 2/)/sub 2/, where is R is Me, ET, or CH/sub 2/SiMe/sub 3/, thermally decompose (60/sup 0/C (10/sup -2/mm)) by elimination of alkane (MeH, EtH, or Me/sub 4/Si, respectively) to yield the bridging carbene compounds. The 1:1 complex with pyridine is described. The related hafnium dialkyls decomposed in a related manner though in this case the decomposition product can only be characterized as its pyridine complex. The NMR spectra of the pyridine complexes of zirconium and hafnium are similar. In contrast, the corresponding titanium compound is thermally stable to 190/sup 0/C. The titanium carbene may be prepared by sodium amalgam reduction of Cl/sub 2/Ti(N(SiMe/sub 3/)/sub 2/)/sub 2/. The crystal structure of the bridging carbene compound of zirconium was determined by single-crystal x-ray crystallography. The crystals were found to be orhtorhombic of space group Pbca, and the cell consists of three, fused planar, four-membered rings giving the molecule a tub configuration. The Zr-C bond distances are 2.16 A, and the Zr-N distances are 2.04 to 2.09 A. 20 references, 4 tables.

Research Organization:
Univ. of California, Berkeley
DOE Contract Number:
AC03-76SF00098
OSTI ID:
6909334
Journal Information:
Organometallics; (United States), Vol. 2:1
Country of Publication:
United States
Language:
English