Chemistry of dinuclear fulvalene complexes. Dihydrides, zwitterions, and ring-slippage complexes, derived from FvM[sub 2](CO)[sub 6] (M = Mo, W)
- Univ. of Oslo (Norway)
- Univ. of California, Berkeley, CA (United States)
- Universitaet Essen (Germany)
Reduction of the metal - metal-bonded complex FvW[sub 2](CO)[sub 6] generated the dianion FvW[sub 2](CO)[sub 6][sup 2[minus]]. An X-ray crystallographic analysis of [Et[sub 4]N[sup +]][sub 2]FvW[sub 2](CO)[sub 6][sup 2[minus]] (monoclinic space group P2[sub 1]/c, a = 7.687(2) [angstrom], b = 13.752(4) [angstrom], c = 16.297(5) [angstrom], [beta] = 94.80(2)[degree], V = 1716.8(8) A[sup 3], Z = 4) showed the dianion to contain a planar Fv ring system bonded to the two metal centers in an anti fashion. The dianion reacted with a number of electrophiles to yield the neutral species FvW[sub 2](CO)[sub 6]E[sub 2] E = H, Me, Et, [sigma]-C[sub 3]H[sub 6], CH[sub 2]Ph. The pK[sub a] values for the two consecutive deprotonations of FvW[sub 2](CO)[sub 6]H[sub 2] were determined as 14.0 and 16.6 by equilibrium measurements in acetonitrile. Thermolysis and photolysis of FvW[sub 2](CO)[sub 6]H[sub 2] yielded FvW[sub 2]-(CO)[sub 6] and H[sub 2]. Unlike Cp[sub 2]W[sub 2](CO)[sub 6], FvW[sub 2](CO)[sub 6] underwent protonation at the W-W bond by HBF[sub 4][center dot]Et[sub 2]O in acetonitrile. Reactions of FvW[sub 2](CO)[sub 6] and FvMo[sub 2](CO)[sub 6] with PMe[sub 3] and Me[sub 2]-PCH[sub 2]PMe[sub 2] (dmpm) resulted in generation of the dinuclear zwitterions FvM[sub 2](CO)[sub 5](PMe[sub 3])[sub 2] and FvM[sub 2](CO)[sub 5](dmpm), respectively. 62 refs., 5 figs., 7 tabs.
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 6970791
- Journal Information:
- Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 13:8; ISSN 0276-7333; ISSN ORGND7
- Country of Publication:
- United States
- Language:
- English
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661300 -- Other Aspects of Physical Science-- (1992-)
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
ACETONITRILE
ANIONS
CHARGED PARTICLES
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPILED DATA
COMPLEXES
CRYSTALLOGRAPHY
DATA
DECOMPOSITION
DIFFRACTION
INFORMATION
IONS
ISOMERS
MAGNETIC RESONANCE
MOLECULAR STRUCTURE
MOLYBDENUM COMPLEXES
NITRILES
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
REDUCTION
RESONANCE
SCATTERING
THERMODYNAMICS
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES
X-RAY DIFFRACTION