Phosphinomethyl complexes of zirconium
The synthesis, structure, and reactivity of a new class of early transition metal complexes containing a phosphinomethyl ligand are described. These complexes possess two different sites of reactivity: the zirconium metal center and the remote phosphine moiety. Phosphinomethyl complexes of zirconium are the first examples of such complexes containing either a group IV or V metal displaying exclusively monohapto bonding between ligand and metal. Zirconcene halides can be selectively mono- or bis-substituted with the appropriate dialkylphosphinomethylithium reagent. The steric and electronic properties of these complexes can be altered by modifying several moieties in the molecule. The intramolecular disposition of the remote functionality can be exploited to stabilize the unusual +3 oxidation state of zirconium. The isolation and characterization of a monomeric paramagnetic phosphinomethyl zirconocene(III) complex has opened the way for a systematic study of the heretofore inaccessible zirconium(III) system. The remote phosphine moiety can also be exploited in an intermolecular manner to construct novel heterobimetallic compounds. These include simple acyclic bridged species as well as a remarkably hindered cyclic complex. Phosphinomethyl complexes of zirconium are unique because they have a remote phosphine moiety which is free to interact in either an inter- or intramolecular fashion. The most important ramifications of this for organic synthesis or catalysis are the stabilization of an unusual monomeric zirconium(III) oxidation state, and the ability to complex a second transition metal to form heterobimetallic complexes.
- Research Organization:
- California Univ., Davis (USA)
- OSTI ID:
- 5599214
- Resource Relation:
- Other Information: Thesis (Ph. D.)
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
METHANE
CHEMICAL PREPARATION
MOLECULAR STRUCTURE
PHOSPHORUS COMPOUNDS
ZIRCONIUM COMPLEXES
ALKANES
COMPLEXES
HYDROCARBONS
ORGANIC COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)