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/
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
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Synthesis of titanium, zirconium, and hafnium complexes that contain diamido donor ligands of the type [(t-BuN-o-C[sub 6]H[sub 4])[sub 2]O][sup 2[minus]] and an evaluation of activated versions for the polymerization of 1-hexene
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
10 SYNTHETIC FUELS
ALKANES
CHEMICAL PREPARATION
STRUCTURAL CHEMICAL ANALYSIS
CARBENES
HAFNIUM COMPLEXES
HETEROCYCLIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
TITANIUM COMPLEXES
ZIRCONIUM COMPLEXES
EXPERIMENTAL DATA
COMPLEXES
DATA
HYDROCARBONS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
RADICALS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
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