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Decarbonylation Products of Binuclear Methylphosphinidene Complexes of Cyclopentadienyliron Carbonyls: Triplet and Quintet Structures Are Favored Energetically over Singlet Structures with Iron-Iron Multiple Bonding.

ABSTRACT: The structures, energetics, and energetically preferred spin states of methylphosphinidene-bridged binuclear cyclopentadienyliron carbonyl complexes MePFe₂(CO)_nCp₂ (n = 4, 3, 2, and 1) related to the experimentally known (μ-RP)Fe₂(μ-CO)(CO)₂Cp₂ (R = cyclohexyl, phenyl, mesityl, and 2,4,6-tBu₃C₆H₂) complexes have been investigated by density functional theory. Singlet structures having a pyramidal pseudotetrahedral phosphorus environment with 18-electron iron configurations are energetically preferred in the tricarbonyl and tetracarbonyl systems MePFe₂(CO)_nCp₂ (n = 4 and 3) with the lowest energy structures of the tricarbonyl very closely resembling the experimentally determined structures. For the more unsaturated dicarbonyl and monocarbonyl systems MePFe₂(CO)_nCp₂ (n = 2 and 1), higher spin state triplet and quintet structures are energetically preferred over singlet structures. These more highly unsaturated structures can be derived from the lowest energy singlet MePFe₂(CO)_nCp₂ (n = 4, 3) by the removal of carbonyl groups. The iron atoms giving up carbonyl groups in their 16- and 14-electron configurations bear the spin density of the unpaired electrons in the higher spin states. The lowest energy singlet structure of the monocarbonyl MePFe₂(CO)Cp₂, although a relatively high energy isomer, is unusual among the collection of MePFe₂(CO)_nCp₂ (n = 4, 3, 2, and 1) structures by having both the formal Fe=Fe double bond and the four-electron donor MeP unit with the planar phosphorus coordination required to allow each of its iron atoms to attain the favored 18-electron configuration.

SUBMITTER: Rudenco O

PROVIDER: S-EPMC10938326 | biostudies-literature | 2024 Mar

REPOSITORIES: biostudies-literature

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Decarbonylation Products of Binuclear Methylphosphinidene Complexes of Cyclopentadienyliron Carbonyls: Triplet and Quintet Structures Are Favored Energetically over Singlet Structures with Iron-Iron Multiple Bonding.

Rudenco Oleg O Lupan Alexandru A Silaghi-Dumitrescu Radu R King R Bruce RB

ACS omega 20240228 10

The structures, energetics, and energetically preferred spin states of methylphosphinidene-bridged binuclear cyclopentadienyliron carbonyl complexes MePFe2(CO)nCp2 (n = 4, 3, 2, and 1) related to the experimentally known (μ-RP)Fe2(μ-CO)(CO)2Cp2 (R = cyclohexyl, phenyl, mesityl, and 2,4,6-tBu3C6H2) complexes have been investigated by density functional theory. Singlet structures having ...[more]

PMID: 38496963

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Project description:The skin is the largest organ in the body and is consistently exposed to aggressive environmental attacks (biological/physical/chemical, etc.). Reactive oxygen species (ROS) are formed during the normal oxidative metabolism which enhances to a lethal level under stress conditions referred to as oxidative stress. While, under normal conditions, cells are capable of dealing with ROS using non-enzymatic and enzymatic defense system, it can lead to a critical damage to cell system via the oxidation of cellular components under stress condition. Lipid peroxidation is a well-established mechanism of cellular injury in all kinds of organisms and it is often used as an indicator of oxidative stress in cells and tissues. In the presence of metal ions, ROS such as hydrogen peroxide (H2O2) produces highly reactive hydroxyl radical (HO•) via Fenton reaction. In the current study, we have used the porcine skin (intact pig ear/skin biopsies) as an ex vivo/in vitro model system to represent human skin. Experimental results have been presented on the participation of HO• in the initiation of lipid peroxidation and thereby leading to the formation of reactive intermediates and the formation of electronically excited species eventually leading to ultra-weak photon emission (UPE). To understand the participation of different electronically excited species in the overall UPE, the effect of a scavenger of singlet oxygen (1O2) on photon emission in the visible and near-infrared region of the spectrum was measured which showed its contribution. In addition, measurement with interference filter with a transmission in the range of 340-540 nm reflected a substantial contribution of triplet carbonyls (3L=O∗) in the photon emission. Thus, it is concluded that during the oxidative radical reactions, the UPE is contributed by the formation of both 3L=O∗ and 1O2. The method used in the current study is claimed to be a potential tool for non-invasive determination of the physiological and pathological state of human skin in dermatological research.

Dataset Information

Decarbonylation Products of Binuclear Methylphosphinidene Complexes of Cyclopentadienyliron Carbonyls: Triplet and Quintet Structures Are Favored Energetically over Singlet Structures with Iron-Iron Multiple Bonding.

Publications

Decarbonylation Products of Binuclear Methylphosphinidene Complexes of Cyclopentadienyliron Carbonyls: Triplet and Quintet Structures Are Favored Energetically over Singlet Structures with Iron-Iron Multiple Bonding.

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