C-C activation of organic small ring compounds by rearrangement of cycloalkylhydridorhodium complexes to rhodacycloalkanes. Synthesis of metallacyclobutanes, including one with a tertiary M-C bond, by nucleophilic addition to. pi. -allyl complexes
In the initial work on C-H activation by the unsaturated fragment ((eta/sup 5/-C/sub 5/Me/sub 5/)Rh(PMe/sub 3/)) the authors observed, as in the case of the iridium analogue, that generation of this fragment in cyclopropane at -60/sup 0/C resulted only in C-H insertion to give a cyclopropyl hydride 1. Subsequently however, they communicated the observation that 1 rearranges by an intramolecular pathway to the rhodacyclobutane 4 in high yield. This observation presented a unique opportunity to study the direct rearrangement of the initial product of C-H activation, an alkyl hydride, to the C-C insertion product. The following describes, a mechanistic study of the rearrangement of 1 to 4 and the limited success in extending the chemistry to cyclobutane. Additionally some related chemistry on the independent synthesis of rhodacyclobutanes is reported.
- Research Organization:
- Lawrence Berkeley Lab., CA
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 6996813
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:23; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
Similar Records
Carbon-hydrogen and carbon-carbon bond activation of cyclopropane by a hydridotris(pyrazolyl)borate rhodium complex
Mechanism of oxidative addition of cyclopentadienyl-rhodium complexes to carbon-hydrogen and carbon-carbon bonds
Related Subjects
400201* -- Chemical & Physicochemical Properties
ALKANES
BUTANE
CHEMICAL BONDS
CHEMICAL PREPARATION
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COMPLEXES
CYCLOALKANES
DATA
EXPERIMENTAL DATA
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
RHODIUM COMPLEXES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
YIELDS