2011
DOI: 10.1021/om200555e
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Photochemistry of CpMn(CO)3 and Related Derivatives: Spectroscopic Observation of Singlet and Triplet CpMn(CO)2

Abstract: We report novel photochemistry derived from (η 5 -C 5 H 5 )Mn(CO) 3 (1a), (η 5 -C 5 H 4 Me)Mn(CO) 3 (1b), (η 5 -C 5 Me 5 )Mn(CO) 3 (1c), and (η 5 -indenyl)Mn(CO) 3 (1d). Photolysis (>261 nm, 1 h) of the parent tricarbonyl (1a−d), matrix isolated in argon at 10 K, yields two species: the expected singlet dicarbonyl 1 (η 5 -L)Mn(CO) 2 ( 1 2a−d) and an additional compound assigned as the triplet dicarbonyl 3 (η 5 -L)Mn(CO) 2 ( 3 2a−d). Density functional theory calculations (B3LYP/LANL2DZ) support the structural … Show more

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Cited by 13 publications
(13 citation statements)
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“…Literature reveals that the cymantrene based half sandwich has the ability to photolytically dissociate a metal carbonyl group creating an electron deficient manganese metal center, which can further be used for derivatization. Additionally, the significant contribution of Mn (I) tricarbonyl type complex for their photo‐triggered CO‐releasing molecular (CORM) behavior[6g] prompted us to investigate the photo‐dissociation mechanism of compound 1 . We, therefore, focused our study to understand the photolytic behavior of compound 1 to introduce the phenomena for light sensing applications.…”
Section: Resultsmentioning
confidence: 99%
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“…Literature reveals that the cymantrene based half sandwich has the ability to photolytically dissociate a metal carbonyl group creating an electron deficient manganese metal center, which can further be used for derivatization. Additionally, the significant contribution of Mn (I) tricarbonyl type complex for their photo‐triggered CO‐releasing molecular (CORM) behavior[6g] prompted us to investigate the photo‐dissociation mechanism of compound 1 . We, therefore, focused our study to understand the photolytic behavior of compound 1 to introduce the phenomena for light sensing applications.…”
Section: Resultsmentioning
confidence: 99%
“…Organometallic fragments like, half sandwich cymantrenyl group are significant moieties because of their three legged piano stool type structure involving carbonyl groups attached to manganese atom and for their unique photolytic decarbonylation property. The photo‐dissociation behavior led to a large number of functional derivatives and showed interesting photophysical phenomena . Recently, a Mn (I) tricarbonyl complex has been investigated as a biocompatible CO releasing molecule (CORM), in which the photolytic behavior is used for the release of CO into the cellular matrices [6g].…”
Section: Introductionmentioning
confidence: 99%
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“…The example of Fe(CO) 4 just discussed above is one case which is particularly well understood. The chemistry of the 16‐electron fragments CpMn(CO) 2 and CpCo(CO), derived from photolysis of the corresponding tri‐ and di‐carbonyl complexes, are two more systems that have received extensive attention …”
Section: Applicationsmentioning
confidence: 99%
“…The chemistry of the 16-electron fragments CpMn(CO) 2 and CpCo(CO), derived from photolysis of the corresponding tri-and di-carbonyl complexes, are two more systems that have received extensive attention. [58][59][60]…”
Section: Applicationsmentioning
confidence: 99%