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Author Trost, B. M. ♦ Merlic, C. A. :
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ♦ ALKENES ♦ ALKYLATION ♦ CYCLOALKANES ♦ KETONES ♦ MOLYBDENUM ♦ CATALYTIC EFFECTS ♦ ACETATES ♦ CATALYSTS ♦ HOMOGENEOUS CATALYSIS ♦ ISONITRILES ♦ LIGANDS ♦ MOLYBDENUM COMPLEXES ♦ NUCLEAR MAGNETIC RESONANCE ♦ SULFONES ♦ SYNTHESIS ♦ ALKANES ♦ CARBONIC ACID DERIVATIVES ♦ CARBOXYLIC ACID SALTS ♦ CATALYSIS ♦ CHEMICAL REACTIONS ♦ COMPLEXES ♦ ELEMENTS ♦ HYDROCARBONS ♦ MAGNETIC RESONANCE ♦ METALS ♦ ORGANIC COMPOUNDS ♦ ORGANIC SULFUR COMPOUNDS ♦ RESONANCE ♦ TRANSITION ELEMENT COMPLEXES ♦ TRANSITION ELEMENTS ♦ Chemical & Physicochemical Properties
Abstract A series of molybdenum complexes bearing {alpha}-diimine, N,N{prime}-diarylideneethylenediamine, and isonitrile ligands have been prepared and evaluated for their ability to catalyze alkylations by using allyl acetates and especially allyl sulfones. (bpy)Mo(CH{sub 3}CN)(CO){sub 3} proved to be a very effective catalyst in contrast to bpyMO(CO){sub 4}. The addition of isonitrile ligands to molybdenum hexacarbonyl generates the most effective molybdenum catalysts known to date. The reactive catalyst proved to be Mo(RNC){sub 4}(CO){sub 2}. With this new catalyst, a much broader range of substrates can be employed including many that failed or reacted very poorly by using molybdenum hexacarbonyl. The regioselectivity also differs from that obtained with molybdenum hexacarbonyl. The stereochemistry of the reaction proceeds with very clean net retention of configuration even under conditions that produced diastereomeric mixtures with molybdenum hexacarbonyl. A mechanistic rationale that accounts for the seemingly disparate complexes that are catalysts is presented.
ISSN 00027863
Educational Use Research
Learning Resource Type Article
Publisher Date 1990-12-19
Publisher Place United States
Journal Journal of the American Chemical Society
Volume Number 112
Issue Number 26


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