Infrared multiphoton dissociation of MC{sub 4}H{sub 6}{sup +} [M = Fe, Co, or Ni; C{sub 4}H{sub 6} = 1,3-butadiene or (C{sub 2}H{sub 2})(C{sub 2}H{sub 4})]

Journal Article · Wed Apr 09 04:00:00 EDT 1997 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja963200c· OSTI ID:535446

Surya, P I; Ranatunga, D R.A.; Freiser, B S ^[1]

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1. Purdue Univ., West Lafayette, IN (United States)

The infrared multiphoton dissociation (IRMPD) of the two isomers, M(1,3-butadiene){sup +} and M(C{sub 2}H{sub 2})-(C{sub 2}H{sub 4}){sup +} (M = Fe, Co, or Ni), was investigated. For the butadiene system, FeC{sub 4}C{sub 6}{sup +} was observed to give three products, CoC{sub 4}H{sub 6}{sup +} four products, and NiC{sub 4}H{sub 6}{sup +} only one product. The observation of four products has not been previously seen in IRMPD studies of ions and suggests a fortuitous balance of several factors. Interestingly, the IRMPD of M(butadiene-1,1,4,4-d{sub 4}){sup +} was observed not only to give one product for M = Fe, Co, or Ni but also to proceed with a decreased photodissociation rate. For the M(C{sub 2}H{sub 2})(C{sub 2}H{sub 4}){sup +} system, IRMPD suggests that D{degree}(Co{sup +}-C{sub 2}H{sub 2}) nearly equals D{degree}(Co{sup +}-C{sub 2}H{sub 4}). Also, SORI and/or competitive CID indicate that D{degree}(M{sup +}-C{sub 2}H{sub 2}) > D{degree}(M{sup +}-C{sub 2}H{sub 4}) by 0.5-2 kcal/mol for M = Fe or Ni. On the basis of these observations, we assign D{degree}(Fe{sup +}-C{sub 2}H{sub 2}) = 36 {+-} 2 kcal/mol, D{degree}(Co{sup +}-C{sub 2}H{sub 2}) = 43 {+-} 2 kcal/mol, and D{degree}(Ni{sup +}-C{sub 2}H{sub 2}) = 45 {+-} 2 kcal/mol. These results are compared to recent theoretical and experimental findings. 27 refs., 4 figs., 5 tabs.

• DOE Contract Number: FG02-87ER13766
• OSTI ID: 535446
• Journal Information: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 14 Vol. 119; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
BUTADIENE
CHEMICAL REACTION KINETICS
COBALT COMPLEXES
DISSOCIATION
EXPERIMENTAL DATA
IRON COMPLEXES
NICKEL COMPLEXES
ORGANOMETALLIC COMPOUNDS
PHOTOCHEMICAL REACTIONS