Reaction of 1,3-butadiene and allene with a diosmacyclobutane
- Colorado State Univ., Fort Collins, CO (United States)
The reaction of the diosmacyclobutane 3 with butadiene gives as a kinetic product the 1,2 adduct Os[sub 2](CO)[sub 8][[mu]-CH[sub 2]CH(CH=CH[sub 2])] (4); the thermodynamic product is an allyl acyl dinuclear complex Os[sub 2](CO)[sub 8]([mu]-C(O)CH[sub 2]-[eta][sup 3]-CH[sub 2]CHCH[sub 2] ) (6), derived from 4 by CO insertion. Photolysis of Os[sub 8](CO)[sub 12] in the presence of butadiene gives 6, Os[sub 2](CO)[sub 7]([mu]-CH[sub 2]-[eta][sup 3]-CH[sub 2]CHCH[sub 2]) (7), and (butadiene)Os(CO)[sub 3] (8). The structure of 7 has been confirmed by X-ray crystallography: orthorhombic, space group P2[sub 1]2[sub 1]2[sub 1], a = 6.928(2) A b = 9.473(2) A, c = 20.683(4) A, V = 1357.4(6) A[sup 3], and Z = 4. The reaction of Na[sub 2][Os[sub 2](CO)[sub 8]] with 3,4-dichloro-1-butene or cis-1,4-dichloro-2-butene gave 7 as the principal product. Neither 4 nor 6 rearranged to 7 under thermal conditions, and attempts to carbonylate 7 to 4 or 6 failed at pressures of up to 120 psig. The reaction of 3 with allene gives as a kinetic product the 1,2 adduct Os[sub 2]-(CO)[sub 8][[mu]-CH[sub 2]C(=CH[sub 2])] (9); the thermodynamic product is Os[sub 2](CO)[sub 8]([mu]-[eta][sup 3]-CH[sub 2]CCH[sub 2]) (10). Photolysis of Os[sub 3](CO)[sub 12] in the presence of allene gives 9, 10, and (allene)Os(CO)[sub 4] (11). Allene is bound more tightly than butadiene to the Os[sub 2](CO)[sub 8] unit. 38 refs., 6 figs., 2 tabs.
- DOE Contract Number:
- FG02-84ER13299
- OSTI ID:
- 6455666
- Journal Information:
- Organometallics; (United States), Vol. 14:2; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ADDUCTS
CHEMICAL PREPARATION
ALLENE
CHEMICAL REACTIONS
BUTADIENE
ORGANOMETALLIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
OSMIUM COMPLEXES
EXPERIMENTAL DATA
NMR SPECTRA
COMPLEXES
DATA
DIENES
HYDROCARBONS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
POLYENES
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400102 - Chemical & Spectral Procedures
400500 - Photochemistry