84583-27-7Relevant articles and documents
Reactivity of acetylenes coordinated to cobalt. 6. Preparation and structure of (μ-C4O2R1R2)(μ-C=CR 3R4)Co2(CO)6 compounds. Unexpected 1,2-shift of the substituents of coordinated haloacetylenes
Horváth, István T.,Pályi, Gyula,Markó, László,Andreetti, Giovanni D.
, p. 1049 - 1053 (2008/10/08)
α-Haloacetylenes react with (μ-butenolido)(μ-carbonyl)hexacarbonyldicobalt(Co-Co) complexes in a reaction involving a 1,2-shift of one of the substituents of the acetylene, to yield almost quantitatively the corresponding (μ-butenolido)(μ-vinylidene)hexacarbonyldicobalt(Co-Co) complex. The crystal and molecular structure of a representative ((μ-C4O2H-n-Pe)(μ-CCI2)Co 2(CO)6 (n-Pe = n-pentyl)) of the new vinylidene complexes was determined by X-ray diffraction: space group P1, a = 1169.7 (6) pm, b = 1130.6 (7) pm, c = 867.5 (4) pm, a = 89.09 (4)°, β = 96.33 (4)°, γ = 105.11 (5)°. The most characteristic features of the structure are the following: the six carbonyl groups are ordered almost symmetrically (C2v), and the lactone ring is rectangular to the Co-Co line and is oriented with its C-C double bond toward the vinylidene ligand, the plane of which is orthogonal to the plane of the lactone ring.
