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• W1965342689 startingPage "366" @default.
• W1965342689 abstract "New consideration of the chemical bonding in [L3M(μ-P3)M′L3]n+ complexes (triple-deckers with bifacial coordination of the unit P3) focuses on the active role played by the P3 σ bonding network. The argument, developed from an extended Hückel molecular orbital (EHMO) analysis, is based largely on the rigorous symmetry properties of the MO interactions. In particular, for 30 electron species, only the in-plane σ bonding orbitals of P3 can match the in-phase metal dn combinations (e′ symmetry for an ideal D34 model). Additionally, an in-phase combination of metal σ-hybrids interacts with the total-symmetric σ bonding MO of P3 (a′1). Only through the latter interactions, are the low lying and empty metal levels partially saturated. On increasing the total electron count, the donor-acceptor interactions of e′ symmetry are reduced and, for 34 electron systems, the attractions transform into electron repulsions without destroying the primary triple-decker assembly. Finally, the role of the P3 σ orbitals is re-examined for some monomeric complexes of the type LnM(η3-P3 and for the white phosphorus molecule (P4) itself. Thus, the variations of the PP bond lengths can be interpreted in terms of a different involvement of the P3 σ orbitals for both the mononuclear and binuclear adducts." @default.
• W1965342689 created "2016-06-24" @default.
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• W1965342689 date "1998-07-01" @default.
• W1965342689 modified "2023-10-13" @default.
• W1965342689 title "The role of cyclo-triphosphorus (P3) in-plane σ orbitals in coordinating transition metal fragments" @default.
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• W1965342689 doi "https://doi.org/10.1016/s0020-1693(97)06066-0" @default.
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