Oxo-hydrido and imido-hydrido derivatives of permethyltantalocene. Structures of (. eta. sup 5 -C sub 5 Me sub 5 ) sub 2 Ta( double bond O)H and (. eta. sup 5 -C sub 5 Me sub 5 ) sub 2 Ta( double bond NC sub 6 H sub 5 )H: Doubly or triply bonded tantalum oxo and imido ligands
- California Inst. of Tech., Pasadena (United States)
The syntheses of the complexes Cp*{sub 2}Ta({double bond}O)H, Cp*{sub 2}Ta({double bond}NH)H and Cp*{sub 2}Ta({double bond}NC{sub 6}H{sub 5})H and the solid-state structures for Cp*{sub 2}Ta({double bond}O)H and Cp*{sub 2}Ta({double bond}NC{sub 6}H{sub 5})H are reported (Cp* = ({eta}{sup 5}-C{sub 5}Me{sub 5})). These are formally 18-electron complexes with the oxo or imido ligands donating only one {pi}-electron pair to tantalum. Since these ligands commonly donate both {pi}-electron pairs (i.e. they triply bond) to transition-metal centers, at issue are the Ta-O and Ta-N bond orders. Cp*{sub 2}Ta({double bond}NC{sub 6}H{sub 5})H crystallizes in the monoclinic space group. The solid-state structure reveals a linear Ta-N-C unit for Cp*{sub 2}Ta({double bond}NC{sub 6}H{sub 5})H. This feature is accommodated on both steric and electronic grounds. Cp*{sub 2}Ta({double bond}O)H crystallizes in the monoclinic space group. The Ta-N and Ta-O bond distances are intermediate between the values expected for double and triple bonds, and the {nu}(Ta-O) for Cp*{sub 2}Ta({double bond}O)H is considerably less than that for other metal oxo compounds. Thus, the tantalum-nitrogen and tantalum-oxygen bond orders for these two compounds are anomalously low.
- DOE Contract Number:
- FG03-85ER13431
- OSTI ID:
- 7227208
- Journal Information:
- Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 31:1; ISSN 0020-1669; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BOND LENGTHS
CATALYSTS
CHEMICAL BONDS
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DENITRIFICATION
DESULFURIZATION
DIFFRACTION
DIMENSIONS
DOUBLE BONDS
KINETICS
LENGTH
LIGANDS
MOLECULAR STRUCTURE
MONOCLINIC LATTICES
REACTION KINETICS
SCATTERING
SYNTHESIS
TANTALUM COMPLEXES
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION