Activation of alkanes with organotransition metal complexes
Alkanes, although plentiful enough to be considered for use as feedstocks in large-scale chemical processes, are so unreactive that relatively few chemical reagents have been developed to convert them to molecules having useful functional groups. However, a recently synthesized iridium (Ir) complex successfully converts alkanes into hydridoalkylmetal complexes. This is a dihydride having the formula Cp/sup */(L)IrH/sub 2/, where Cp/sup */ = (CH/sub 3/)/sub 5/C/sub 5/ and L = (CH/sub 3/)/sub 3/P/sub 3/, respectively. Irradiation with ultraviolet light causes the dihydride to lose H/sub 2/, generating the reactive intermediate Cp/sup */IrL, which reacts rapidly with C-H bonds in every molecule so far tested (including alkanes) and leads to hydridoalkyliridium complexes Cp/sup */(L)Ir(R)(H). Evidence has been obtained that this C-H insertion, or oxidative addition, reaction proceeds through a simple three-center transition state and does not involve organic free radicals as intermediates. Thus the intermediate Cp/sup */IrL reacts most rapidly with C-H bonds having relatively high bond energies, such as those at primary carbon centers, in small organic rings, and in aromatic rings. The hydridoalkyliridium products of the insertion reactions can be converted into functionalized organic molecules - alkyl halides - by treatment with mercuric chloride followed by halogens. Expulsion (reductive elimination) of the hydrocarbon from the hydridoalkyliridium complexes can be induced by Lewis acids or heat, regenerating the reactive intermediate Cp/sup */IrL. Oxidative addition of the corresponding rhodium complexes Cp/sup */RhL to alkane C-H bonds has also been observed, although the products formed in this case are much less stable and undergo reductive elimination at -20/sup 0/C.
- Research Organization:
- Univ. of California, Berkeley
- OSTI ID:
- 5939815
- Journal Information:
- Science (Washington, D.C.); (United States), Journal Name: Science (Washington, D.C.); (United States) Vol. 223; ISSN SCIEA
- Country of Publication:
- United States
- Language:
- English
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ALKANES
CATALYTIC EFFECTS
CHEMICAL ACTIVATION
COMPLEXES
ELECTROMAGNETIC RADIATION
HYDROCARBONS
HYDROGEN PRODUCTION
IRIDIUM COMPLEXES
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
RADIATIONS
TRANSITION ELEMENT COMPLEXES
ULTRAVIOLET RADIATION