Cobalt/Mercury Carbide Clusters Based on Trigonal-Prismatic or Octahedral Co6C Skeletons − X-ray Crystal Structure of (NEt4)2[Co6C(CO)12{HgW(CO)3Cp}2]

Abstract

The anionic transition metal clusters (NEt 4 3 Cp, Mo(CO) 3 Cp, Fe(CO) 2 Cp, Co(CO) 4 , Mn(CO) 5 ] (x = 13 or 15) have been obtained by reaction of the corresponding octahedral (x = 13) or trigonal-prismatic (x = 15) cobalt carbido carbonyl clusters with the mercury [a] 1243 derivatives ClHgM. Metal skeleton rearrangements and some redox processes have been found to be induced by varying both the temperature and the solvent, resulting in new compounds containing tetra-or hexacoordinated mercury atoms.

The Redox Chemistry of [Co6C(CO)15]2–: A Synthetic Route to New Co-Carbide Carbonyl Clusters

“…In theory, an 86 CVE [Co 6 C(CO) 12 ] 4– might exist, but in view of its very high negative charge, it is probably readily oxidized to the paramagnetic trianion. Even if the free [Co 6 C(CO) 12 ] 4– tetra-anion has not been observed, some of its derivatives stabilized by Au(I) or Hg(II) fragments have been previously isolated, for example, [Co 6 C(CO) 12 ­(AuPPh 3 ) 2 ] 2– and [Co 6 C(CO) 12 {μ 3 -HgW(CO) 3 Cp} 2 ] 2– . , …”