Electronic and vibrational spectroscopy in a nematic liquid crystal solvent. Band polarizations of binuclear metal carbonyls

Levenson, Robert A.; Gray, Harry B.; Ceasar, Gerald P.

doi:10.1021/ja00715a018

Cited by 106 publications

(46 citation statements)

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“…25 The absence of bridging ligands in Mn 2 (CO) 10 means that, unlike the halide clusters, the system relies solely on the metal -metal bond for its integrity. As a result, these systems are rather prone to photodissociation following σ σ * transitions.…”

Section: 24mentioning

confidence: 99%

Electronic Structure of Metal—Metal Bonds

McGrady

2005

Encyclopedia of Inorganic Chemistry

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Section: 24mentioning

confidence: 99%

Electronic Structure of Metal—Metal Bonds

McGrady

2005

Encyclopedia of Inorganic Chemistry

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“…The widely used assignments of transitions in dinuclear complexes [34][35][36][37][38][39][40] follow the designation suggested by Levenson et al [35] for [Mn 2 (CO) 10 ] which exists in the non-bridged form. The intense, near-UV band (around 340 nm) was ascribed to sAEs * transition (where s denotes metal-metal bond) based on the intensity, polarization and energy criteria.…”

Section: Calculated Spectramentioning

confidence: 99%

Structure, Spectroscopy and Photochemistry of the [M(η5-C5H5)(CO)2]2 Complexes (M=Fe, Ru)

Jaworska

Macyk

Stasicka

2004

Structure and Bonding

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The structures of all possible isomeric forms of the [M(h 5 -C 5 H 5 )(CO) 2 ] 2 complexes (M=Fe, Ru) are calculated with the use of the DFT method. The results indicate that both dimers can occur in three stable forms: bridged trans and cis and non-bridged trans. Contrary to the previous reports, the cis non-bridged form turns out to be an unstable transition state. Instead, an additional stable structure, a gauche non-bridged one, is found but only in the case of the Ru compound. Without any outer-sphere interaction the trans-bridged form is of the lowest energy for both dimers. The results are compared with the experimental data. Strong impact of the medium on the stability of the individual structures in solution is emphasized. The electronic spectra of all stable forms, calculated using TDDFT method, reproduce well spectral properties of both complexes. Moreover, they are useful in interpreting the medium effect and photochemical behaviour. The photoreactivity is briefly reviewed pointing at analogies and differences between the Fe and Ru complexes.

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“…Irradiation of Co 2 (CO) 8 at low temperature has been shown to lead to loss of CO, equation (9), and the reaction is…”

Section: Ru-rumentioning

confidence: 99%

“…Reaction according to equation (9) leads to the suggestion that dissociative loss of CO can become the dominant photoreaction when the cage effect becomes severe enough to preclude separation of the 17-valeace electron radicals.…”

Section: C(co)mentioning

confidence: 99%