14878-28-5Relevant articles and documents
The structure and reactivity of phenylacetylene-derived metallacycles containing cobalt and mercury
Tyler, Stephen J.,Burlitch, James M.
, p. 231 - 247 (1989)
The crystal structure of the product of the reaction of phenylacetylene and Hg[Co(CO)4]2, viz. (C6H5)2C4H3[Co(CO)2HgCo(CO)4]2 (1) was determined by X-ray diffraction (space group C2/c; Z = 8; R = 0.051; a 22.08, b 11.62, c 28.08 A; β 114.78°) to be a C4Co2-containing dimetallacycle the cobaltcobalt bond distance of which (2.548(3) A) is asymmetrically bridged by the mercury atom of an HgCo(CO)4 moiety. The three-coordinate, bridging mercury atom, Hg(2), is 2.553(2) A from the π-bonded cobalt and 2.641(2) A from the σ-bonded cobalt of the metallacycle. This bridged Hg is compared to the semi-bridging CO in the iron metallacycles, Fe2(CO)6(C4R4)2. The two-coordinate mercury, Hg(1), of the second HgCo(CO)4 group is 2.475(2) A from the σ-bonded cobalt fo the metallacycle. Symmetrization reaction of 1 gave previously known Hg{Co2(CO)4(C6H5C2H)2[Hg-Co(CO)4]}2 (2), the structure of which was also determined by X-ray diffraction (space group P1; Z = 1; R = 0.065' a 11.448, b 12.757, c 10.353 A; α 94.37, β 75.49, γ 66.87°). Compound 2 contains two [HgCo(CO)4]-bridged metallacyclic units symmetrically disposed about a third Hg atom. The metal-metal distances of compound 2 are similar to those in 1. Sodium amalgam reduction of 1 gave, in addition to NaCo(CO)4, an anion postulated to be [(CO)2Co(η5-C5H2(C6H5)2O)]- (3) on the basis of its reaction with acetyl chloride to give 1-acetoxy-2,5-diphenyl-cyclopentadienyldicarbonylcobalt (4). Although no reaction was observed with acetic acid, treatment of 3 with trifluoroacetic acid produced a hydroxy-derivative, 5 analogous to the acetoxy compound, 4.
Alkylcobalt carbonyls. 10. CO activation and phase-transfer-active coordination sites in organocobalt carbonyls. Mechanism of the reaction of benzyl halides and tetracarbonylcobaltate (-I)
Haász, Ferenc,Bartik, Tamás,Galamb, Vilmos,Pályi, Gyula
, p. 2773 - 2779 (2008/10/08)
(4′-Halomethyl-1′,2′-benzo)-15-crown-5 (RX, 1; X = Cl (a), I (b)) compounds were reacted with Na-[Co(CO)4] (2). The corresponding η1-RC(O)Co(CO)4 (5), η1-RCo(CO)4 (6), and η3-RCo(CO)3 (7) derivatives were obtained through intermediates [(η5-RX)Na][Co(CO)4] (3) and [(η5-Na+)RC(O)Co(CO)3(X-)] (4). The reactions leading to 7 from 1 were found to be reversible. Derivatives of 4 and 5 were prepared by monosubstitution with PPh3, giving 8 and 9, respectively. The reversibility of the reaction of PhCH2Cl with 2 was also demonstrated.
Synthesis and Properties of Na3-C3H5Fe(NO)(CO)CN> and η3-C3H5Fe(NO)(CO)CNMe (η3-C3H5 = Allyl)
Moll, Matthias,Behrens, Helmut,Seibold, Hans-Juergen,Merbach, Peter
, p. 409 - 410 (2007/10/02)
The allyl iron complexes η3-C3H5Fe(NO)(CO)L (L = CN(-), CNMe) can be obtained by the reaction of η3-C3H5Fe(NO)(CO)2 with NaN(SiMe3)2 and subsequent methylation. - Keywords: Allyl Nitrosyl Carbonyl, Cyano, Isonitrile Iron Complexes
