Cluster Complexes with Bonds Between Transition Elements and Zinc, Cadmium, and Mercury

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]

“…The selected ClHgM species [M ϭ W(CO) 3 Cp, Mo(C-O) 3 Cp, Fe(CO) 2 Cp, Co(CO) 4 , Mn(CO) 5 ] were reacted separately with the NEt 4 ϩ salts of the anions [Co 6 C(CO) 15 ] 2Ϫ (1) and [Co 6 C(CO) 13 ] 2Ϫ (2) (see Scheme 1).…”

“…Ϫ The compounds ClHgM [20] [M ϭ Mo(CO) 3 Cp, W(CO) 3 Cp, Fe(CO) 2 Cp, Co(CO) 4 , Mn(CO) 5 ], (NEt 4 ) 2 [Co 6 C(CO) 15 ], [6] and (NEt 4 ) 2 [Co 6 C(CO) 13 ] [3] were synthesized as described previously. The synthetic methodology detailed in this section corresponds to the reactions described in Scheme 1 that afforded better yields and pure final products.…”

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]

“…[1] Two-centre two-electron bonding is found only for the simplest bi-and trimetallic compounds. [2] In comparison with other transition metals, only very few cobalt/mercury systems have been reported to date. This is surprising because cobalt and rhodium, for example, are unique in forming two hexanuclear anions with different metal frameworks, the octahedral [M 6 C(CO) 13 ] 2Ϫ (86 EC) and the trigonal-prismatic [M 6 C(CO) 15 ] 2Ϫ (90 EC), which can be interconverted through the uptake and release of carbon monoxide.…”

“…In fact, the reaction of 3 with ClHgM in a 1:1 molar ratio yielded a highly insoluble material that could not be characterized, along with the trimetallic species HgM 2 . The formation of these two products can be rationalized in terms of a rapid ligandredistribution process of the initially formed [Co 6 C(CO) 15 (HgM) 2 ]. This result is in agreement with our predictions that the neutral mercury/transition metal clusters should be unstable with regard to the symmetrization process, while the negatively charged species should be reasonably stable and hence isolable in most cases.…”

Heterometallic Osmium−Mercury Chain Structures Linking Two {Os3(CO)10(μ-X)} Subunits (X = Cl, Br, I): Syntheses and Molecular Structures of [{Os3(CO)10(μ-X)}2(μ4-Hg)] (X = Cl, I), [{Os3(CO)10(μ-Cl)}2{μ-HgOs(CO)4}2], andcis-[Os(CO)4{(μ-Hg)Os3(CO)10(μ-Cl)}2]

“…Organomercurials play an important role in the syntheses of osmium−mercury mixed-metal clusters of various nuclearities, − presumably because mercury atom can attach readily to a variety of main group and transition metal frameworks. − The polar osmium−mercury bonds in these compounds may trigger further chemical changes or core manipulations especially at the interface of different metallic domains. A representative example is the isolation and characterization of [Os 18 Hg 3 C 2 (CO) 42 ] 2- from which stepwise demercuriation of the central mercury atoms has yielded the complete series [Os 18 Hg x C 2 (CO) 42 ] y - ( x = 1−3, y = 1−4) via photochemical and redox chemical reactions. , Furthermore, interesting solution dynamics associated with the mercury fragments in a number of Os−Hg mixed-metal clusters have been reported. ,, Variable-temperature NMR investigations of clusters of the type [{M 3 } 2 Hg] indicated that a μ 2 -Hg bridging moiety possesses about the same mobility as a μ 2 -hydrido ligand …”