The First Example of a Seven-Coordinate Vanadium(III) Thiolate Complex Containing the Hydrazine Molecule, an Intermediate of Nitrogen Fixation

Abstract

The first example of a seven-coordinate vanadium(III) thiolate complex, [V(PS3' ')(N(2)H(4))(3)] (1), where PS3' ' = [P(C(6)H(3)-3-Me(3)Si-2-S)(3)](3)(-), has been synthesized and characterized. Compound 1 contains a tetradentate ligand (PS3' ') and three hydrazine molecules, forming a capped octahedral geometry. A five-coordinate vanadium(III) complex, [V(PS3)(1-Me-Im)] (2), where PS3 = [P(C(6)H(4)-2-S)(3)](3)(-) and 1-Me-Im = 1-methyl-imidazole, was also obtained. Compound 2 adopts a trigonal bipyramidal geometry, in which the vanadium is ligated by the title ligand, PS3, and one 1-Me-Im molecule.

Synthesis and structural characterization of dimolybdenum(IV) and molybdenum(VI) complexes with trisbenzenethiolatophosphine ligands

“…Electronic spectra were recorded at the range of 300-1100 nm on Hewlett-Packard 8453 spectrophotometer. 1 H and 31 P-{ 1 H} NMR measurements were performed on a BRUKER AMX-400 at ambient temperature. The resonance positions are reported with positive shifts downfield of SiMe 4 as calculated from the residual solvent peaks ( 1 H) or downfield of external 85% H 3 PO 4 ( 31 P).…”

“…To continue our efforts on studying the chemistry of thiofunctional metal complexes relevant to biological processes, we have extended our interest to molybdenum chemistry [1]. The chemistry of molybdenum-sulfur complexes has drawn much attention due to its biological significance [2][3][4].…”

“…To elucidate how molybdenum sites in these two enzymes participate in these relevant biological reactions, it is advantageous to explore the basic coordination chemistry of molybdenum, particularly, in a ligation environment similar to the enzymes. To this end, we utilize trisbenzenethiolatophosphines, PS3 and PS3 00 , as title ligands which were first developed by ZubietaÕs laboratory and have been investigated in other metal chemistry [1,[7][8][9][10][11][12][13][14][15][16]. In the reaction of molybdenum with these tetradentate ligands, two high valent molybdenum complexes, [Mo 2 (PS3) 2 (PS3H)] (1) and [Mo(PS3 00 ) 2 ] (2), were obtained.…”

Exploring secondary-sphere interactions in Fe–NxHycomplexes relevant to N2fixation

“…16 Examples of secondary sphere interactions in M–N x H y species are known for other transition metals as well. 17 …”

Aminocarboxylate complexes of vanadium(III): Electronic structure investigation by high-frequency and -field electron paramagnetic resonance spectroscopy

“…This was explained further by Meier et al in terms of the geometric requirements of seven-vs. six-coordination with the former requiring a bite angle that would severely strain a six-membered chelate ring [24]. However, in previous studies of V(III) complexes with a tripodal PS3 ligand and its derivatives (PS3 = trisbenzenethiolatophosphine) by some of us, it was found that the geometries of V(III) complexes are very flexible with little relevance of the size of the chelate ring [43]. Furthermore, the crystal structure of a seven-coordinate complex of sexidentate trdta with Mn(II), [Mn(trdta)(H 2 O)] 2À , has been recently reported [44].…”