Radical formation during an attempted photochemical substitution reaction of η5-C5Me5Os(CO)2CH2Ph

Johnston, Laura; Baird, Michael C.

doi:10.1016/0022-328x(88)87094-3

Cited by 9 publications

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“…Although (η 5 -C 5 H 5 ) 2 Os 2 (CO) 4 , III , was first reported almost 40 years ago, we were surprised by the complete absence of photochemical studies in the literature. Indeed the only photochemical study of a derivative of III appears to be that of Johnson and Baird, who have shown that solution photolysis of (η 5 -C 5 Me 5 )Os(CO) 2 CH 2 Ph in the presence of PMe 2 Ph results in the formation of exo -(η 4 -C 5 Me 5 CH 2 Ph)Os(CO) 2 PMe 2 Ph by what was believed to be a radical mechanism. The paucity of photochemical studies is certainly due to the expense of the osmium starting materials and the difficulties associated with the synthesis of III and its derivatives.…”

Section: Introductionmentioning

confidence: 99%

Solution and Nujol Matrix Photochemistry of (η⁵-C₅H₅)₂Os₂(CO)₄ and Nujol Matrix Photochemistry of (η⁵-C₅H₄CH₃)₂Ru₂(CO)₄ and (η⁵-C₅H₅)M(CO)₂H, Where M = Ru and Os

2001

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Lowering the temperature of a Nujol solution of (η 5 -C 5 H 4 CH 3 ) 2 Ru 2 (CO) 4 containing bands of the trans-and cis-bridging and trans-nonbridging isomers from room temperature to ca. 90 K results in complete disappearance of the bands of the trans-terminal isomer. The photochemistry of (η 5 -C 5 H 4 CH 3 ) 2 Ru 2 (CO) 4 in frozen Nujol at 90 K differs subtly from that of (η 5 -C 5 H 5 ) 2 Ru 2 (CO) 4 in inert gas matrixes at 12 K in that the trans-bridging isomer is found to undergo photolysis at high energy (λ irr > 250 nm) to yield both the triply bridged carbonylloss species, (η 5 -C 5 H 4 CH 3 ) 2 Ru 2 (µ-CO) 3 , and the cis-bridged species isomer. There is no evidence for formation of the trans-nonbridged isomer upon photolysis as observed for (η 5 -C 5 H 5 ) 2 Ru 2 (CO) 4 . The solution photochemistry of (η 5 -C 5 H 5 ) 2 Os 2 (CO) 4 is shown to closely parallel that of (η 5 -C 5 H 5 ) 2 Ru 2 (CO) 4 . Photolysis of (η 5 -C 5 H 5 ) 2 Os 2 (CO) 4 in CHCl 3 yields (η 5 -C 5 H 5 )Os(CO) 2 Cl, while photolysis in benzene yields hydride products believed to arise from metal-to-ring coupling of radicals. Photolysis of (η 5 -C 5 H 5 ) 2 Os 2 (CO) 4 , which exists only in a nonbridged form, in frozen Nujol (90 K) results in CO loss and formation of (η 5 -C 5 H 5 ) 2 Os 2 -(µ-CO) 3 as the only photoproduct. Photolysis of (η 5 -C 5 H 5 )M(CO) 2 H, where M ) Ru or Os, in frozen Nujol yields (η 5 -C 5 H 5 )M(CO)H and a second product that appears to be either (η 5 -C 5 H 6 )M(CO) 2 or the (η 5 -C 5 H 5 )M(CO) 2 radical.

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Section: Introductionmentioning

confidence: 99%

Solution and Nujol Matrix Photochemistry of (η⁵-C₅H₅)₂Os₂(CO)₄ and Nujol Matrix Photochemistry of (η⁵-C₅H₄CH₃)₂Ru₂(CO)₄ and (η⁵-C₅H₅)M(CO)₂H, Where M = Ru and Os

2001

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Annual survey of ruthenium and osmium for the year 1988

Richmond

1991

Journal of Organometallic Chemistry

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Multiply substituted cyclopentadienyl metal complexes: I. Solid-state and solution conformational studies on

Plooy

Toit

Levendis

et al. 1996

Journal of Organometallic Chemistry

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Radical formation during an attempted photochemical substitution reaction of η5-C5Me5Os(CO)2CH2Ph

Cited by 9 publications

References 9 publications

Solution and Nujol Matrix Photochemistry of (η⁵-C₅H₅)₂Os₂(CO)₄ and Nujol Matrix Photochemistry of (η⁵-C₅H₄CH₃)₂Ru₂(CO)₄ and (η⁵-C₅H₅)M(CO)₂H, Where M = Ru and Os

Solution and Nujol Matrix Photochemistry of (η⁵-C₅H₅)₂Os₂(CO)₄ and Nujol Matrix Photochemistry of (η⁵-C₅H₄CH₃)₂Ru₂(CO)₄ and (η⁵-C₅H₅)M(CO)₂H, Where M = Ru and Os

Annual survey of ruthenium and osmium for the year 1988

Multiply substituted cyclopentadienyl metal complexes: I. Solid-state and solution conformational studies on

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Radical formation during an attempted photochemical substitution reaction of η5-C5Me5Os(CO)2CH2Ph

Cited by 9 publications

References 9 publications

Solution and Nujol Matrix Photochemistry of (η5-C5H5)2Os2(CO)4 and Nujol Matrix Photochemistry of (η5-C5H4CH3)2Ru2(CO)4 and (η5-C5H5)M(CO)2H, Where M = Ru and Os

Solution and Nujol Matrix Photochemistry of (η5-C5H5)2Os2(CO)4 and Nujol Matrix Photochemistry of (η5-C5H4CH3)2Ru2(CO)4 and (η5-C5H5)M(CO)2H, Where M = Ru and Os

Annual survey of ruthenium and osmium for the year 1988

Multiply substituted cyclopentadienyl metal complexes: I. Solid-state and solution conformational studies on

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Solution and Nujol Matrix Photochemistry of (η⁵-C₅H₅)₂Os₂(CO)₄ and Nujol Matrix Photochemistry of (η⁵-C₅H₄CH₃)₂Ru₂(CO)₄ and (η⁵-C₅H₅)M(CO)₂H, Where M = Ru and Os

Solution and Nujol Matrix Photochemistry of (η⁵-C₅H₅)₂Os₂(CO)₄ and Nujol Matrix Photochemistry of (η⁵-C₅H₄CH₃)₂Ru₂(CO)₄ and (η⁵-C₅H₅)M(CO)₂H, Where M = Ru and Os