Bonding situation and stability of η1- and η6-bonded heteroarene complexes M(η1-EC5H5)6 and M(η6-EC5H5)2 (M=Cr, Mo, W; E=N, P, As, Sb, Bi)

Synthesis, structure and reactivity of complexes containing a transition metal–bismuth bond

“…Similar studies were carried out using the heteroarene ligand C 5 H 5 Bi, which can also bond to metal centres via 1 -or 6 -bonding modes, giving pseudo-octahedral -bonded compounds or -bonded sandwich compounds [187]. Group 6 transition metal compounds [M( 1 -C 5 H 5 Bi) 6 ] (68) and [M( 6 -C 5 H 5 Bi) 2 ] (M = Cr, Mo, W) (69) were analysed using density functional theory calculations (BP86/TZ2P level) and energy decomposition analysis and showed the M-Bi bonding in the 1 species to be similar in nature to M-CO bonding in the corresponding hexacarbonyl species.…”

Ferracarborane Benzene Complexes [(η-9-L-7,8-C2B9H10)Fe(η-C6H6)]+ (L = SMe2, NMe3): Synthesis, Reactivity, Electrochemistry, Mössbauer Effect Studies, and Bonding

“…The bond dissociation energy is D normale = − false( normalΔ E int + normalΔ E prep false) where Δ E prep (the fragment preparation energy) is the energy that is necessary to promote the fragments from their equilibrium geometry and electronic ground state to the geometry and electronic state that they have in the optimized structure. This method has already proven its usefulness for the analysis of the nature of metal−ligand bonding in ferrocene and some other sandwich compounds. ,, …”

[Re(CO)3Cl(C5H4ClP)2] and [Re(CO)2Cl(C5H4ClP)3]: synthesis and characterization of two novel rhenium(i) phosphinine complexes

“…These ndings suggest strong s-donor as well as p-acceptor character of the phosphinine ligands, which also has been noted before for other systems. [27][28][29] The carbonyl vibrations in the IR spectra show a strong shi from n CO ¼ 1983, 2046, 2155 cm À1 of the precursor [Re(CO) 5 Cl] to n CO ¼ 1924, 1965 cm À1 of complex 2, illustrating again the pronounced s-donating character of the phosphinine and the chlorido ligand. 25,26 The shi from n CO ¼ 1945, 1992, 2046 cm À1 of 1 to n CO ¼ 1924, 1965 cm À1 of 2 further supports the more pronounced s-donating character of phosphinine ligands compared to carbonyls, resulting in increased back-bonding of the metal center to the remaining carbonyl ligands.…”