Remote functionalization of C-H and C-C bonds by naked transition-metal ions (Cosi Fan Tutte)

Journal Article · Tue Aug 01 04:00:00 EDT 1989 · Accounts of Chemical Research; (USA)

DOI:https://doi.org/10.1021/ar00164a004· OSTI ID:7196948

Schwarz, H ^[1]

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1. Universitaet Berlin (Germany, F.R.)

Gas-phase experiments with naked transition-metal ions offer a unique opportunity to probe, in the absence of any solvation, ion-pairing, and/or ligand effects, the intrinsic properties of reactive organometallic species and to evaluate the potential role these remarkable transients play in the initial steps of the activation of C-H and C-C bonds. Not surprisingly, this topic is of fundamental interest in catalysis and has attracted considerable attention in the last decade. The authors and later others, have recently demonstrated that remote functionalization can be achieved in the gas phase for quite a variety of flexible substrates including aliphatic nitriles, isonitriles, amines, alcohols, ketones, alkynes, and allenes, respectively. Specifically, we have shown that the C-H bond of a terminal methyl group of an alkyl chain can be oxidatively added to the anchored transition-metal ion M{sup +} (Scheme II). The insertion is followed by a {beta}-hydrogen shift (5 {yields} 6) or {beta}-cleavage of the C-C bond (5 {yields} 7) to generate intermediates from which eventually reductive elimination of H{sub 2} of ligand detachment occurs. This discussion will be confined to recent results from our laboratory. While most of the data will be concerned with the chemistry of aliphatic nitriles, the reactions of alkynes with bare transition-metal ions will be briefly mentioned.

• OSTI ID: 7196948
• Journal Information: Accounts of Chemical Research; (USA), Journal Name: Accounts of Chemical Research; (USA) Vol. 22:8; ISSN ACHRE; ISSN 0001-4842
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKYNES
CHARGED PARTICLES
CHEMICAL BONDS
CHEMICAL REACTIONS
COMPLEXES
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
IONS
NITRILES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
TRANSITION ELEMENT COMPLEXES