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- W1985370204 abstract "X-Ray structural studies on the redox pair trans-[Mn(CN)(CO)(dppm)2](dppm = Ph2PCH2PPh2) and trans-[Mn(CN)(CO)(dppm)2][PF6]·CH2Cl2 showed that one-electron oxidation results in changes consistent with depopulation of an orbital involved in Mn–P π-back bonding. The ESR spectra of trans-[Mn(CN)(CO)(dppm)2]+, [Mn(CO)(CNCH2CHCH2)(dppm)2]2+, trans-[Mn(CN)(CO)2(PEt3)(dppe)]+(dppe = Ph2CH2CH2PPh2) and trans-[MnBr(CO)2(PEt3)(dppe)]+ in frozen dichloromethane–dichloroethane (1:1) solutions at 90 K, and extended-Hückel molecular-orbital calculations on the model compounds [Mn(CN)(CO)(H2PCH2PH2)2]+, [Mn(CO)(CNMe)(H2PCH2PH2)2]2+, cis- and trans-[Mn(CN)(CO)2(PH3)3]+ and trans-[MnBr(CO)2(PH3)3]+, showed that the semi-occupied molecular orbital of these low-spin octahedral cyanomanganese(II) carbonyls is always primarily manganese dπ in character and in the plane of the phosphorus ligands, either aligned along the Mn(CN) axis as in trans-[Mn(CO)2(PEt3)(dppe)]+ or perpendicular to this axis as in trans-[Mn(CN)(CO)(dppm)2]. The relative arrangement of the cyanide and carbonyl ligands is shown to control the extent of spin delocalisation onto the cyanide ligand." @default.
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- W1985370204 date "1993-01-01" @default.
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- W1985370204 title "Structure and bonding in low-spin octahedral manganese(II) carbonyls: ligand-set control of spin delocalisation" @default.
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- W1985370204 doi "https://doi.org/10.1039/dt9930003103" @default.
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