Carbon-hydrogen and carbon-carbon bond activation of cyclopropane by a hydridotris(pyrazolyl)borate rhodium complex
- Univ. of Rochester, NY (United States). Dept. of Chemistry
Generation of the 16-electron fragment {l_brace}[HB(3,5-dimethylpyrazolyl){sub 3}]Rh(CNCH{sub 2}CMe{sub 3}){r_brace} (Tp{prime}RhL) in the presence of cyclopropane results in C-H activation of the hydrocarbon. The cyclopropyl hydride complex rearranges in benzene solvent to the metallacyclobutane complex Tp{prime}Rh(CNCH{sub 2}CMe{sub 3})(CH{sub 2}CH{sub 2}CH{sub 2}). Thermolysis of the rhodacyclobutane complex produces an {eta}{sup 2}-propylene complex. The related complex Tp{prime}Rh(CN-2,6-xylyl)(C{sub 2}H{sub 4}) has been structurally characterized and displays {eta}{sup 3}-Tp{prime} coordination, both in the solid state and in solution. Thermolysis of the rhodacyclobutane complex in the presence of neopentyl isocyanide leads to insertion of isocyanide into both Rh-C bonds of the metallacycle. Cyclobutane undergoes C-H but not C-C bond cleavage.
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- FG02-86ER13569
- OSTI ID:
- 315969
- Journal Information:
- Organometallics, Vol. 17, Issue 20; Other Information: PBD: 28 Sep 1998
- Country of Publication:
- United States
- Language:
- English
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