Reaction of Cp{sup *}(CO){sub 2}Re=Re(CO){sub 2}Cp{sup *} with dimethyl acetylenedicarboxylate produces a 3,4-dimetallacyclobutene which undergoes photochemical isomerization to a 2,4-dimetallabicyclo[1.1.0]butane
Journal Article
·
· Journal of the American Chemical Society
- Univ. of Wisconsin, Madison, WI (United States)
The reaction of Cp{sup *}(CO){sub 2}Re=Re(CO){sub 2}Cp{sup *} (1) with dimethyl acetylenedicarboxylate (DMAD) produced the 3,4-dimetallacyclobutene Cp{sup *}(CO){sub 2}Re({mu}-{eta}{sup 1},{eta}{sup 1}-CH{sub 3}O{sub 2}CC = CCO{sub 2}CH{sub 3})Re(CO){sub 2}Cp{sup *} (2). Photochemical rearrangement of 2 produced Cp{sup *}(CO){sub 2}Re({mu}-{eta}{sup 2},{eta}{sup 2}-CH{sub 3}O{sub 2}CC = CCO{sub 2}CH{sub 3})Re(CO){sub 2}Cp{sup *} (3), in which both Cp{sup *}(CO){sub 2}Re units are coordinated to the alkyne. Upon heating at 72{degree}C, 3 was converted (t{sub 1/2} = 120 min) to a 78:22 equilibrium mixture of 2:3. Photolysis of 3 in a Rayonet photoreactor (maximum emission 300 nm) resulted in CO loss and formation of Cp{sup *}(CO)Re({mu}-{eta}{sup 2},{eta}{sup 2}-CH{sub 3}O{sub 2}CC = CCO{sub 2}CH{sub 3})({mu}-CO)Re(CO)Cp{sup *} (4). Compounds 2, 3, and 4 were characterized by X-ray crystallography. 36 refs., 6 figs., 3 tabs.
- OSTI ID:
- 232450
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 7 Vol. 118; ISSN JACSAT; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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