Abstract
Saouma, Muller, and Peters recently (J. Am. Chem. Soc., 2009) reported the synthesis of several diiron complexes with two types of bridging diazene HN═NH ligands, designated μ-η1:η1 (bridging end-on) and μ-η2:η2 (bridging side-on), with tridentate phosphine {XBPR3} ligands ({XBPR3} = XB(CH2PR2)3−; X = Ph; R = Ph, CH2Cy). In the present study the energies, optimized geometries, and vibrational frequencies of these complexes with X = H and R = H, CH3, CF3 were obtained theoretically, and the electronic structures were analyzed in terms of iron−diazene donor−acceptor interactions. Natural bond orbital analysis indicates that both bridging end-on and side-on diazenes possess strong π-acceptor properties, which cause significant occupation of their antibonding π*(N−N) LUMOs and weakening of the N−N bonds as the result of coordination. The most pronounced weakening was obtained in complexes with bridging side-on diazene, where interaction of iron d-AOs with π*(N−N) orbitals of the diazene ligands results in the...
Published Version
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