Mechanistic study of the photofragmentation of the clusters [Os3(CO)10(diene)] (diene = cis- 1,3-butadiene, 1,3-cyclohexadiene): Direct observation of the open-triangle primary photoproduct with nanosecond time-resolved infrared and UV-Vis spectroscopy

Maarten J. Bakker; Frank W. Vergeer; František Hartl; Omar S. Jina; Xue Zhong Sun; Michael W. George

doi:10.1016/S0020-1693(99)00560-5

Mechanistic study of the photofragmentation of the clusters [Os₃(CO)₁₀(diene)] (diene = cis- 1,3-butadiene, 1,3-cyclohexadiene): Direct observation of the open-triangle primary photoproduct with nanosecond time-resolved infrared and UV-Vis spectroscopy

Maarten J. Bakker, Frank W. Vergeer, František Hartl, Omar S. Jina, Xue Zhong Sun, Michael W. George

Department of Chemical and Environmental Engineering

Research output: Journal Publication › Article › peer-review

Abstract

The photochemistry of the clusters [Os₃(CO)₁₀(diene)] (diene = cis-1,3-butadiene, 1,3-cyclohexadiene) was studied in detail. Upon near-UV irradiation photofragmentation occurs to give mononuclear [Os(CO)₃(diene)]. The second fragmentation product [Os₂(CO)₇] was trapped by reaction with CO, or with alkenes at low temperatures, to produce the dinuclear complexes [Os₂(CO)₇(L)₂] (L = CO, ethene, 1-octene). The fragmentation was studied further with nanosecond time-resolved UV-Vis and IR spectroscopy and was found to proceed via the initial formation of a triosmium photoproduct with a lifetime of about 100 ns in hexane. From the spectroscopic data we infer that this intermediate has a coordinatively unsaturated open-triangle structure with two bridging carbonyl groups, one bridging the split (CO)₄Os-Os(CO)₂(diene) bond. (C) 2000 Elsevier Science S.A.

Original language	English
Pages (from-to)	597-603
Number of pages	7
Journal	Inorganica Chimica Acta
Volume	300-302
DOIs	https://doi.org/10.1016/S0020-1693(99)00560-5
Publication status	Published - 30 Apr 2000

Keywords

Diene complexes
Osmium complexes
Photochemistry
Triosmium complexes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/S0020-1693(99)00560-5

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Bakker, M. J., Vergeer, F. W., Hartl, F., Jina, O. S., Sun, X. Z., & George, M. W. (2000). Mechanistic study of the photofragmentation of the clusters [Os₃(CO)₁₀(diene)] (diene = cis- 1,3-butadiene, 1,3-cyclohexadiene): Direct observation of the open-triangle primary photoproduct with nanosecond time-resolved infrared and UV-Vis spectroscopy. Inorganica Chimica Acta, 300-302, 597-603. https://doi.org/10.1016/S0020-1693(99)00560-5

Bakker, Maarten J. ; Vergeer, Frank W. ; Hartl, František et al. / Mechanistic study of the photofragmentation of the clusters [Os₃(CO)₁₀(diene)] (diene = cis- 1,3-butadiene, 1,3-cyclohexadiene) : Direct observation of the open-triangle primary photoproduct with nanosecond time-resolved infrared and UV-Vis spectroscopy. In: Inorganica Chimica Acta. 2000 ; Vol. 300-302. pp. 597-603.

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title = "Mechanistic study of the photofragmentation of the clusters [Os3(CO)10(diene)] (diene = cis- 1,3-butadiene, 1,3-cyclohexadiene): Direct observation of the open-triangle primary photoproduct with nanosecond time-resolved infrared and UV-Vis spectroscopy",

abstract = "The photochemistry of the clusters [Os3(CO)10(diene)] (diene = cis-1,3-butadiene, 1,3-cyclohexadiene) was studied in detail. Upon near-UV irradiation photofragmentation occurs to give mononuclear [Os(CO)3(diene)]. The second fragmentation product [Os2(CO)7] was trapped by reaction with CO, or with alkenes at low temperatures, to produce the dinuclear complexes [Os2(CO)7(L)2] (L = CO, ethene, 1-octene). The fragmentation was studied further with nanosecond time-resolved UV-Vis and IR spectroscopy and was found to proceed via the initial formation of a triosmium photoproduct with a lifetime of about 100 ns in hexane. From the spectroscopic data we infer that this intermediate has a coordinatively unsaturated open-triangle structure with two bridging carbonyl groups, one bridging the split (CO)4Os-Os(CO)2(diene) bond. (C) 2000 Elsevier Science S.A.",

keywords = "Diene complexes, Osmium complexes, Photochemistry, Triosmium complexes",

author = "Bakker, {Maarten J.} and Vergeer, {Frank W.} and Franti{\v s}ek Hartl and Jina, {Omar S.} and Sun, {Xue Zhong} and George, {Michael W.}",

year = "2000",

month = apr,

day = "30",

doi = "10.1016/S0020-1693(99)00560-5",

language = "English",

volume = "300-302",

pages = "597--603",

journal = "Inorganica Chimica Acta",

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Bakker, MJ, Vergeer, FW, Hartl, F, Jina, OS, Sun, XZ & George, MW 2000, 'Mechanistic study of the photofragmentation of the clusters [Os₃(CO)₁₀(diene)] (diene = cis- 1,3-butadiene, 1,3-cyclohexadiene): Direct observation of the open-triangle primary photoproduct with nanosecond time-resolved infrared and UV-Vis spectroscopy', Inorganica Chimica Acta, vol. 300-302, pp. 597-603. https://doi.org/10.1016/S0020-1693(99)00560-5

Mechanistic study of the photofragmentation of the clusters [Os₃(CO)₁₀(diene)] (diene = cis- 1,3-butadiene, 1,3-cyclohexadiene): Direct observation of the open-triangle primary photoproduct with nanosecond time-resolved infrared and UV-Vis spectroscopy. / Bakker, Maarten J.; Vergeer, Frank W.; Hartl, František et al.
In: Inorganica Chimica Acta, Vol. 300-302, 30.04.2000, p. 597-603.

Research output: Journal Publication › Article › peer-review

TY - JOUR

T1 - Mechanistic study of the photofragmentation of the clusters [Os3(CO)10(diene)] (diene = cis- 1,3-butadiene, 1,3-cyclohexadiene)

T2 - Direct observation of the open-triangle primary photoproduct with nanosecond time-resolved infrared and UV-Vis spectroscopy

AU - Bakker, Maarten J.

AU - Vergeer, Frank W.

AU - Hartl, František

AU - Jina, Omar S.

AU - Sun, Xue Zhong

AU - George, Michael W.

PY - 2000/4/30

Y1 - 2000/4/30

N2 - The photochemistry of the clusters [Os3(CO)10(diene)] (diene = cis-1,3-butadiene, 1,3-cyclohexadiene) was studied in detail. Upon near-UV irradiation photofragmentation occurs to give mononuclear [Os(CO)3(diene)]. The second fragmentation product [Os2(CO)7] was trapped by reaction with CO, or with alkenes at low temperatures, to produce the dinuclear complexes [Os2(CO)7(L)2] (L = CO, ethene, 1-octene). The fragmentation was studied further with nanosecond time-resolved UV-Vis and IR spectroscopy and was found to proceed via the initial formation of a triosmium photoproduct with a lifetime of about 100 ns in hexane. From the spectroscopic data we infer that this intermediate has a coordinatively unsaturated open-triangle structure with two bridging carbonyl groups, one bridging the split (CO)4Os-Os(CO)2(diene) bond. (C) 2000 Elsevier Science S.A.

AB - The photochemistry of the clusters [Os3(CO)10(diene)] (diene = cis-1,3-butadiene, 1,3-cyclohexadiene) was studied in detail. Upon near-UV irradiation photofragmentation occurs to give mononuclear [Os(CO)3(diene)]. The second fragmentation product [Os2(CO)7] was trapped by reaction with CO, or with alkenes at low temperatures, to produce the dinuclear complexes [Os2(CO)7(L)2] (L = CO, ethene, 1-octene). The fragmentation was studied further with nanosecond time-resolved UV-Vis and IR spectroscopy and was found to proceed via the initial formation of a triosmium photoproduct with a lifetime of about 100 ns in hexane. From the spectroscopic data we infer that this intermediate has a coordinatively unsaturated open-triangle structure with two bridging carbonyl groups, one bridging the split (CO)4Os-Os(CO)2(diene) bond. (C) 2000 Elsevier Science S.A.

KW - Diene complexes

KW - Osmium complexes

KW - Photochemistry

KW - Triosmium complexes

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U2 - 10.1016/S0020-1693(99)00560-5

DO - 10.1016/S0020-1693(99)00560-5

M3 - Article

AN - SCOPUS:0034732519

SN - 0020-1693

VL - 300-302

SP - 597

EP - 603

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

ER -

Bakker MJ, Vergeer FW, Hartl F, Jina OS, Sun XZ, George MW. Mechanistic study of the photofragmentation of the clusters [Os₃(CO)₁₀(diene)] (diene = cis- 1,3-butadiene, 1,3-cyclohexadiene): Direct observation of the open-triangle primary photoproduct with nanosecond time-resolved infrared and UV-Vis spectroscopy. Inorganica Chimica Acta. 2000 Apr 30;300-302:597-603. doi: 10.1016/S0020-1693(99)00560-5