The synthesis and characterization of [IMesH]+[(η3-C5H5)V(N)Cl2]−: An anionic vanadium(v) complex with a terminal nitrido ligand

Abstract

A series of new half-sandwich vanadium complexes have been prepared. The structures of two new anionic vanadium half-sandwich complexes, [CpVCl(3)](-) and [CpV(N)Cl(2)](-) are presented. (15)N isotopic labelling studies have been conducted to unambiguously assign the V[triple bond, length as m-dash]N infra red stretching frequencies of both a neutral and an anionic (cyclopentadienyl)vanadium nitrido complex. The influence of strongly pi-basic coligands on the hapticity of the cyclopentadienyl ligands in half-sandwich complexes of vanadium is discussed.

Mesoionic Carbenes in Low- to High-Valent Vanadium Chemistry

“…The formation of the desired vanadium(III) complex was initially evident by the strong paramagnetic nature of its 1 H NMR, revealing an effective magnetic moment of 2.71 μ B , which is in line with the presence of a d 2 electron configuration and is comparable to previously reported vanadium(III) complexes. 109 Despite numerous attempts and due to the high sensitivity of the complex, only low-quality crystals of the complex could be obtained from concentrated diethyl ether solutions at −40 °C. In any case, the connectivity of the molecule was unambiguously determined, confirming the vanadium(III) oxidation state ( Figure 6 , left).…”

Photo-activation of d0 niobium imido azides: en route to nitrido complexes

“…[8][9][10] Surprisingly, niobium and tantalum nitride complexes have received little attention and, to the best of our knowledge, no neutral mononuclear Nb nitride complex is known. To-date, formation of group 5 metal nitrides mostly relies on the reaction of low-valent organometallic precursors (isolated or formed in situ) with N 2 , [11][12][13][14][15][16] azides, [17][18][19][20][21] or cyanate 22 as the N-atom source (Scheme 1). Recently, Sita also reported formation of a dinuclear Ta(V) bis(m-nitrido) complex from chemical reduction of a Ta(V) hydrazido species.…”

The structure and chemistry of tris(pentafluorophenyl)borane protected mononuclear nitridotitanium complexes

“…The ν(TiuN) stretch is tentatively assigned to a signal at 976 cm −1 by comparison to the work of Abernethy and coworkers; a peak close to this wavenumber is found for all the nitridoborane complexes reported herein. 14 Once crystalline, 4 is poorly soluble in simple chlorinated and aromatic solvents and spectroscopic analysis was conducted in 4 : 1 deuterated benzene/1,2-difluorobenzene. The 1 H NMR spectrum has characteristic doublets for the two dimethylamine environments at δ 2.46 and 1.87 ppm, which are assigned to the cation and anion, respectively.…”

“…For example, Abernethy and co-workers have recently succeeded in isolating and determining the structure of a terminal vanadium nitride through the combination of a cyclopentadienyl ligand with a bulky and strongly donating N-heterocyclic carbene supporting ligand (Structure V, Chart 1). [14][15][16][17] A complementary approach to preventing the formation of dimers or coordination polymers is to cap the nitrido nitrogen with a Lewis acid. 18,19 Tris( pentafluorophenyl)borane is ideally suited because of its strong Lewis acidity, favourable steric profile and relatively unreactive B-C bonds.…”