123882-19-9Relevant articles and documents
Syntheses and NMR spectra of Co3(CO)9[μ3-CCHAr2] clusters derived from DDT and related molecules: X-ray crystal structures of [[bis(4-chlorophenyl)methyl]carbynyl]tricobalt nonacarbonyl and of its bis(4-chloronaphthyl) analogue
Gates, Reginald A.,D'Agostino, Michael F.,Sutin, Karen A.,McGlinchey, Michael J.,Janik, Thomas S.,Churchill, Melvyn Rowen
, p. 20 - 26 (2008/10/08)
The reaction of Co2(CO)8 with a series of 1,1,1-trichloro-2,2-bis(aryl)ethanes yields the corresponding Co3(CO)9[μ3-CCHAr2] tetrahedral clusters, where Ar = 4-chlorophenyl (3), 4-methoxyphenyl (4), or 4-chloronaphthyl (6). Co3(CO)9[μ3-CCH(p-C6H 4Cl)2] (3) crystallizes in the monoclinic space group P21/n with a = 13.0834 (27) A?, b = 14.2224 (16) A?, c = 14.1649 (24) A?, β = 95.871 (15)°, V = 2621.9 (8) A?3, and Z = 4; treatment of all 3434 unique data led to final values of RF = 3.7% and RwF = 3.3%. (RF = 2.5% and RwF = 3.0% for those 2781 data with |Fo| > 6σ(|Fo|).) The chloronaphthyl cluster of Co3(CO)9[μ3-CCH(C10H 6Cl)2] (6) crystallizes in the triclinic space group P1 with a = 8.839 (3) A?, b = 12.156 (4) A?, c = 16.513 (5) A?, α = 105.974 (25)°, β = 92.280 (25)°, γ = 115.512 (22)°, V = 1513.57 (84) A?3, and Z = 2; treatment of the 3620 unique data led to final values of RF = 4.8% and RwF = 5.3%. At -120°C, the cobalt carbonyl ligands of the phenyl clusters 3 and 4 exhibit a 6:3 splitting in their 13C NMR spectra; however, the naphthyl cluster 6 does not show this effect. These data are discussed in terms of the ability of the aryl groups to obstruct the fluxionality of the cobalt carbonyl ligands.
