A laser flash photolysis, matrix isolation, and DFT investigation of (η6-C6H5Y)Cr(CO)3 (Y=NH2, OCH3, H, CHO, or CO2CH3)

Alamiry, Mohammed A. H.; Brennan, Peter A.; Long, Conor; Pryce, Mary T.

doi:10.1016/j.jorganchem.2008.06.003

Cited by 11 publications

(22 citation statements)

References 33 publications

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“…peaks at 1898 and 1971 cm -1 . Photoproduct bands are evident at 1846 and 1907 cm -1 assigned to (h 6 -Aniline)Cr(CO) 2 (CH 4 ) as observed previously [26]. In addition, a broad asymmetric feature in the region where uncoordinated CO absorbs (circa 2135 cm -1 ) confirms the photo-induced decarbonylation of (h-Aniline)Cr(CO) 3 .…”

Section: Low Temperature Matrix Isolationsupporting

confidence: 81%

“…We have also reported a significant difference between the photochemical behaviour of (h 6 -Benzene)Cr(CO) 3 in room temperature solution when compared to low temperature frozen gas matrixes [26]. In room temperature n-heptane solution, photolysis at 400 nm depleted the n CO bands of (h 6 -Benzene)Cr (CO) 3 and produced n CO bands of an excited state species [(h 6 -Benzene)Cr(CO) 3 ]* which ejects CO over 150 ps to produce (h 6 -Benzene)Cr(CO) 2 .…”

Section: Introductionmentioning

confidence: 63%

“…Failure to observe (h 6 -Benzene)Cr(CO) 2 formation at 12 K was explained by proposing the existence of a small thermal barrier to CO-loss from the [(h 6 -Benzene)Cr(CO) 3 ]* excited state species which could not be surmounted at 12 K following 405 nm irradiation [25]. However no explanation was available for the lack of photoproduct n CO bands despite the substantial depletion of (h 6 -Benzene)Cr(CO) 3 in these experiments [26].…”

Section: Introductionmentioning

confidence: 82%

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Matrix effects and their role in the low-temperature photochemistry of (η-Aniline)Cr(CO)3

Alamiry

Long

Fidgeon

et al. 2010

Journal of Organometallic Chemistry

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Section: Low Temperature Matrix Isolationsupporting

confidence: 81%

Section: Introductionmentioning

confidence: 63%

Section: Introductionmentioning

confidence: 82%

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Matrix effects and their role in the low-temperature photochemistry of (η-Aniline)Cr(CO)3

Alamiry

Long

Fidgeon

et al. 2010

Journal of Organometallic Chemistry

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“…Long and co-workers have recently reported a series of photoactive 'half sandwich' compounds of the type [(η 6 -arene)Cr(CO) 3 ] (figure 3), where arene = benzene, aniline, benzaldehyde, anisole, thioanisole, methylbenzoate, naphthalene, phenanthrene [20][21][22].…”

Section: (B) Photochemistry Of Trans(xx)-[ru(x) 2 (Co) 2 (Bpy)]mentioning

confidence: 99%

“…For example, TD-DFT results for [(η 6 -methylbenzoate)Cr(CO) 3 ] and [(η 6 -benzaldehyde)Cr(CO) 3 ] indicate that the nature of the excited states is less polarized between MACT and MCCT states [20]. That is, both CO loss and ring slip process occur at all excitation wavelengths.…”

Section: (B) Photochemistry Of Trans(xx)-[ru(x) 2 (Co) 2 (Bpy)]mentioning

confidence: 99%

The photochemistry of transition metal complexes using density functional theory

Garino

Salassa

2013

Phil. Trans. R. Soc. A.

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The use of density functional theory (DFT) and timedependent DFT (TD-DFT) to study the photochemistry of metal complexes is becoming increasingly important among chemists. Computational methods provide unique information on the electronic nature of excited states and their atomic structure, integrating spectroscopy observations on transient species and excited-state dynamics. In this contribution, we present an overview on photochemically active transition metal complexes investigated by DFT. In particular, we discuss a representative range of systems studied up to now, which include CO-and NO-releasing inorganic and organometallic complexes, haem and haem-like complexes dissociating small diatomic molecules, photoactive anti-cancer Pt and Ru complexes, Ru polypyridyls and diphosphino Pt derivatives.

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TDDFT modeling of the CO‐photolysis of Fe₂(S₂C₃H₆)(CO)₆, a model of the [FeFe]‐hydrogenase catalytic site

Bertini

Greco

Fantucci

et al. 2014

Int J of Quantum Chemistry

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Upon irradiation with ultraviolet wavelengths, Fe 2 (S 2 C 3 H 6 )(CO) 6 , a simple model of the [FeFe]-hydrogenase active site, undergoes CO dissociation to form the unsaturated Fe 2 (S 2 C 3 H 6 )(CO) 5 species and successively a solvent adduct at the vacant coordination site. In the present work, the CO-photolysis of Fe 2 (S 2 C 3 H 6 )(CO) 6 was investigated by density functional theory (DFT) and timedependent DFT (TDDFT). Trans Fe 2 (S 2 C 3 H 6 )(CO) 5 form and the corresponding trans heptane or acetonitrile solvent adducts are the lowest energy ground state forms. CO dissociation barriers computed for the lowest triplet state are roughly halved with respect to those for the ground state suggesting that some lowlying excited potential energy surface (PES) could be loosely bound with respect to FeAC bond cleavage. The TDDFT excited state PESs and geometry optimizations for the excited states likely involved in the CO-photolysis suggest that the FeAS bond elongation and the partial isomerization toward the rotated form could take place simultaneously, favoring the trans CO photodissociation.

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A laser flash photolysis, matrix isolation, and DFT investigation of (η6-C6H5Y)Cr(CO)3 (Y=NH2, OCH3, H, CHO, or CO2CH3)

Cited by 11 publications

References 33 publications

Matrix effects and their role in the low-temperature photochemistry of (η-Aniline)Cr(CO)3

Matrix effects and their role in the low-temperature photochemistry of (η-Aniline)Cr(CO)3

The photochemistry of transition metal complexes using density functional theory

TDDFT modeling of the CO‐photolysis of Fe₂(S₂C₃H₆)(CO)₆, a model of the [FeFe]‐hydrogenase catalytic site

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A laser flash photolysis, matrix isolation, and DFT investigation of (η6-C6H5Y)Cr(CO)3 (Y=NH2, OCH3, H, CHO, or CO2CH3)

Cited by 11 publications

References 33 publications

Matrix effects and their role in the low-temperature photochemistry of (η-Aniline)Cr(CO)3

Matrix effects and their role in the low-temperature photochemistry of (η-Aniline)Cr(CO)3

The photochemistry of transition metal complexes using density functional theory

TDDFT modeling of the CO‐photolysis of Fe2(S2C3H6)(CO)6, a model of the [FeFe]‐hydrogenase catalytic site

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TDDFT modeling of the CO‐photolysis of Fe₂(S₂C₃H₆)(CO)₆, a model of the [FeFe]‐hydrogenase catalytic site