ISSN:
0009-2940
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Carbonyl Monoolefin Derivatives of the Group VI Transition Metals, III. Preparation and Reaction and Reactivity of Tricarbonyl Chelate Phosphane Olefin DerivativesMonoolefin complexes M(CO)3(R2PC2H4PR2)(ol) (M = Cr, Mo, W; R = CH3, C6H5; ol = maleic anhydride, dimethyl fumarate, dimethyl maleate, methyl acrylate, ethylene, styrene, norbornene) are obtained photochemically from the tetracarbonyl chelate phosphane derivatives. Facial complexes are formed primarily, some of which rearrange intramolecularly to the meridional isomers. The substitution of the olefin proceeds via a dissociative mechanism, the meridional isomers rearrange back to the facial ones prior to the rupture of the metal-olefin bond.
Notes:
Monoolefin-Komplexe M(CO)3(R2PC2H4PR2)(ol) (M = Cr, Mo, W; R = CH3, C6H5; ol = Maleinsäureanhydrid, Dimethylfumarat, Dimethylmaleat, Methylacrylat, Ethylen, Styrol, Norbornen) sind photochemisch aus den Tetracarbonyl-Chelatphosphan-Derivaten zugänglich. Es entstehen zunächst faciale Komplexe, die sich zum Teil rasch intramolekular in die meridionalen Isomeren umlagern. Die Substitution des Olefins verläuft nach einem dissoziativen Mechanismus, der Spaltung der Metall-Olefin-Bindung geht bei den meridionalen Derivaten die intramolekulare meridional-facial-Isomerisierung voraus.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19821151114
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