108150-19-2Relevant articles and documents
Bis(indenyl)vanadium(II): Its oxidation and carbonylation of its cation
Bocarsly, Jeffrey R.,Floriani, Carlo,Chiesi-Villa, Angiola,Guastini, Carlo
, p. 1871 - 1875 (2008/10/08)
The sandwich complex Ind2V (Ind = η5-C9H7) was synthesized, and the formation of its one-electron-ionization product and the carbonylation of its cation were studied. Ind2V itself appears to have a structure analogous to that of other members of the bis(cyclopentadienyl)vanadium family. The oxidation of Ind2V with iodine gave the corresponding vanadium(III) derivative, Ind2V(I) which is paramagnetic by two electrons (μeff = 2.67 μB at 294 K). Ind2V(I) may be carbonylated in the presence of a suitable anion to form the dicarbonyl cation Ind2V(CO)2+. The structures of the monoiodo product and the dicarbonyl cation were determined by X-ray analysis. The indenyl ring in both cases exhibits slippage away from the pure η5-configuration toward a η3-arrangement, a phenomenon that has been observed in a variety of indenyl-containing complexes. Crystallographic details for (η5-C9H7)2V(I): space group P21/n (monoclinic), a = 8.186 (1) A?, b = 12.494 (2) A?, c = 15.025 (2) A?; β = 95.48 (1)°, V = 1529.7 (4) A?3, Z = 4, Dcalcd = 1.772 g cm-3. The final R factor for 1940 observed reflections was 0.037. Crystallographic details for [(η5-C9H7)2V(CO) 2+][BPh4-]: space group P21/n (monoclinic), a = 11.278 (1) A?, b = 16.146 (2) A?, c = 21.381 (5) A?, β = 102.46 (1)°, V = 3802 (1) A?3, Z = 4, Dcalcd = 1.273 g cm-3. The final R factor for 2100 observed reflections was 0.060.
