Binuclear cyclopentadienylrhenium hydride chemistry: terminal versus bridging hydride and cyclopentadienyl ligands

Abstract

Theoretical studies predict the lowest energy structures of the binuclear cyclopentadienylrhenium hydrides Cp2Re2H n (Cp = η(5)-C5H5; n = 4, 6, 8) to have a central doubly bridged Re2(μ-H)2 unit with terminal η(5)-Cp rings and the remaining hydrides as terminal ligands. However, the lowest energy Cp2Re2H2 structure by more than 12 kcal mol(-1) has one terminal η(5)-Cp ring, a bridging η(3),η(2)-Cp ring, and two terminal hydride ligands bonded to the same Re atom. The lowest energy hydride-free Cp2Re2 structure is a perpendicular structure with two bridging η(3),η(2)-Cp rings. The previously predicted bent singlet Cp2Re2 structure with terminal η(5)-Cp rings and a formal Re-Re sextuple bond lies ∼37 kcal mol(-1) above this lowest energy (η(3),η(2)-Cp)2Re2 structure. The thermochemistry of the CpReH n and Cp2Re2H n systems is consistent with the reported synthesis of the permethylated derivatives Cp*ReH6 and Cp*2Re2H6 (Cp* = η(5)-Me5C5) as very stable compounds. Additionally, natural bond orbital analysis, atoms-in-molecules and overlap population density-of-state in AOMIX were applied to present the existence of rhenium-rhenium multiple bonds.

Binuclear cyclopentadienylosmium hydride chemistry: A stable quadruply bridged structure

“…The DFT methods are similar to those used in our previous work with cyclopentadienylrhenium hydrides [15]. We report here our results with the mononuclear CpOsH n (n = 5, 3, 1) and the binuclear Cp 2 Os 2 H n (n = 8, 6, 4, 2) systems as well as the hydride-free Cp 2 Os 2 system.…”

Metal–metal bonding in biscycloheptatrienyl dimetal compounds of the second‐row transition metals

“…Analysis of the frontier bonding molecular orbitals indicated a formal Os–Os quintuple bond ( σ + 2 π + 2 δ ) in singlet (η 5 C 5 H 5 ) 2 Os 2 and a formal Re–Re sextuple bond (2 σ + 2 π + 2 δ ) in singlet (η 5 C 5 H 5 ) 2 Re 2 , thereby giving the metals in both molecules the favored 18‐electron metal configurations. However, subsequent studies showed that isomeric perpendicular M 2 (µ‐C 5 H 5 ) 2 structures (M = Re, Os) with bridging C 5 H 5 rings have considerably lower energies, so that these metal–metal multiply bonded species are not likely to be realized experimentally.…”