Molecular orbital calculations of binuclear systems of Fe, Co and Ni derivatives of pentalene, s-indacene and as-indacene

Bonding and electronic structure of Cp*2Ru2(B8H14), a metallaborane analogue of dinuclear pentalene complexes

“…The Cp derivative exhibits slightly shorter RueC(pentalene) and longer RueC(Cp) distances compared to its Cp* relative. Unsurprisingly, their electronic structure is very similar to that calculated previously for Cp 2 Fe 2 (C 8 H 6 ) [6,7] and other related isoelectronic species [7,9], as exemplified by the MO diagram of Cp 2 Ru 2 (C 8 H 6 ) shown in Fig. 3 (left side).…”

“…The (moderately) low energy of the a g LUMO in the pentalene derivatives originates not only from the its non-bonding interaction with the occupied p orbitals of the pentalenediide ligand (Fig. 2), but also from its stabilization with the p* LUMO of the pentalenediide ligand [6] (not shown in Fig. 2 …”

Metal–Metal Electronic Coupling in syn and anti Stereoisomers of Mixed‐Valent (FeCp)2‐, (RhL2)2‐, and (FeCp)(RhL2)‐as‐Indacenediide Ions

“…The crystallographic geometry of anti‐ [{Fe(Cp)} 2 (μ‐η 5 :η 5 ‐ as ‐indacenediide)] was fully optimised at the B3LYP level of theory (see Experimental Section). The calculation converged to the C 2 ‐symmetric structure of anti ‐ Fe 2 21. The most significant interatomic distances and angles are reported in Table 5, together with the corresponding experimental values.…”

Molecular conformations and π-hydrogen bonds in anti- and syn-binuclear Rh(I) complexes of as-indacene-diide: a computational study

“…In II PO , the HOMO derives from the HOMO À 1 of indacene dianion of symmetry b (C 2 symmetry labels are employed) with two contributions from a filled and an empty orbital of the metallic fragments with rhodium d xz and d yz character. In II FO , the HOMO is principally derived from the HOMO and HOMO À 2 of indacene dianion, both of symmetry a [24], with two contributions from a filled and an empty orbital of the metallic fragments with rhodium d x2 À y2 and d xz character.…”

“…The metals of these complexes belong mainly to groups 6-10. A computational study on s-and as-Ic complexes of Fe, Co and Ni was presented by Manriquez and coworkers [24], who interpreted qualitatively the trends in the metal hapticity by EHMO calculations.…”