Oxidation Products of Vanadocene and of Its Permethylated Analogue, Including the Isolation and the Reactivity of the Unsolvated [VCp₂]⁺Cation

Abstract

The one-electron oxidation of vanadocene, VCp 2 , by [FeCp 2 ] + in toluene affords the 14-electron [VCp 2 ] + cation, which has been isolated as an unsolvated species for the first time. Vanadium hexacarbonyl reacts with VCp 2 to give the µ-isocarbonyl derivative Cp 2 V(µ-OC)V-(CO) 5 as a transient species, which has been characterized in solution by IR analysis. By reaction of VCp 2 with V( 13 CO) 6 followed by treatment with 12 CO, the ionic dicarbonyl derivative [VCp 2 ( 12 CO) 2 ][V( 13 CO) 6 ] is formed, thus showing that during the formation of the ionic compound no redistribution of the carbonyl ligands between the two metal centers occurs. Bis(cyclopentadienyl)vanadium(II) and Co 2 (CO) 8 give Cp 2 VCo(CO) 4 , which slowly decomposes in solution even at low temperature to give [VCp 2 (CO) 2 ][Co(CO) 4 ], which was identified by conventional methods, including single-crystal X-ray diffraction. The reactivity of the unsolvated [VCp 2 ] + cation as well as that of the heterobimetallic compound containing vanadium and cobalt with several Lewis bases is reported.

Metal Telluride Clusters Composed of Niobocene Carbonyl, Telluride, and Cobalt Carbonyl Units: Syntheses, Structures, and Reactivity

“…Angles in the same range have been found in the related compounds [Cp* 2 M(CO) 2 ] (M Ti, Zr, Hf) [12] 4 ]. [13] Recrystallisation of the dark precipitate described above from acetonitrile gave dark crystals with differing morphology. Under the microscope it was possible to distinguish prisms and needles and to separate some of them for X-ray crystallography.…”

Understanding the Reactivity and Basicity of Zeolites: A Periodic DFT Study of the Disproportionation of N2O4 on Alkali‐Cation‐Exchanged Zeolite Y

“…So recrystallization of red‐violet ionic complex 7 was not successful. In contrast to that, vanadocenium tetraphenylborate ( 9 ), prepared by the reaction of 4 with ferrocenium tetraphenylborate,20 is passably soluble in thf. But when 5 was added directly to 9 , an amorphous powder precipitated, too.…”

“…2,2′‐Bipyridyl ( 5 ) was purchased from Merck. Vanadocene ( 4 )21 and vanadocenium tetraphenylborate ( 9 )20 were prepared according to literature procedures.…”

Metal Telluride Clusters — From Small Molecules to Polyhedral Structures

“…The omnipresence of the [Cp* 2 Nb(CO) 2 ] + cation in the structures of compounds 19 − 22 is striking. The remarkably stable Nb III derivative extends the series of dicarbonyl early transition metallocene complexes, for example [Cp* 2 M(CO) 2 ] (M = Ti, Zr, Hf)50 and [(C 5 H 5 ) 2 V(CO) 2 ] + 51. Furthermore, it takes the role of an organometallic template in the formation of cluster anions.…”