Non-oxido divanadium(iv) and divanadium(v) thiolate complexes with a new type of chalcogenide bridging motif

Abstract

In our effort to study vanadium chalcogenide chemistry, we have synthesized and characterized a class of non-oxido divanadium(IV) and divanadium(V) complexes with chalcogenide and dichalcogenide as bridges. All structures consist of a similar divanadium motif, in which two metal centers are bridged by one μ-chalcogenide and one μ-η(2):η(2)-dichalcogenide, forming a V2(μ-E)(μ-η(2):η(2)-E2) (E = S or Se) core structure. These compounds are [V(IV)2(PS3)2(μ-Se2)(μ-Se)][PPh4]2 (1), [V(V)2(PS3'')2(μ-Se2)(μ-Se)] (2), [V(V)2(PS3'')2(μ-S2)(μ-S)] (3a) and [V(V)2(PS3)2(μ-S2)(μ-S)] (3b) ([PS3](3-) = P(C6H4-2-S)3 and [PS3''](3-) = P(C6H3-3-SiMe3-2-S)3). Compound 1 exhibits diamagnetic behavior, indicating strong antiferromagnetic coupling between two d(1) centers. Compounds 2 and 3a-b have the highest oxidation states for vanadium ions (+5/+5) among those reported divanadium chalcogenide clusters. The work demonstrates that high-valent divanadium chalcogenide clusters can be obtained with the activation of elemental chalcogens by low-valent vanadium ions.

A non-oxo methanolate-bridged divanadium(IV) complex with tris(2-sulfanidylphenyl)phosphane ligands: synthesis, structural characterization and magnetic investigation

“…The S1-V1-O1, S2-V1-O2 and S3-V1-O1 angles (Table 2) are much smaller from those in an ideal octahedron (the axis angle is 180 ), but closer to those in a trigonal antiprism (Notni et al, 2009). The bond lengths of (I) are very similar to those in previously reported non-oxide divanadium complexes, [V 2 (-E)(-2 : 2 -E 2 )(PS3) 2 ] n (E = S or Se, n = 0 or 2À, and PS3 indicates a PS3 00 derivative) (Wu et al, 2015). The VÁ Á ÁV separation in (I) is 2.8989 (14) Å , which is similar to the values seen in [V 2 (-E)(-2 : 2 -E 2 )(PS3) 2 ] n complexes (2.90-3.08 Å ).…”

“…In comparison, non-oxo high-valent vanadium complexes are relatively scarce (Hsu et al, 2006) and the chemistry of these complexes has been of interest and has been investigated in our laboratory. We have utilized a tris(2sulfanidylphenyl)phosphane ligand system to obtain a class of non-oxo divanadium complexes containing chalcogenide bridges (Wu et al, 2015). In a continuation of this research, a ISSN 2053ISSN -2296 # 2016 International Union of Crystallography non-oxo divanadium(IV) complex with methanolate bridges has been synthesized and characterized, namely tetraphenylphosphonium tri--methanolato-bis({tris[2-sulfanidyl-3-(trimethylsilyl)phenyl]phosphane}vanadium(IV)) methanol disolvate, (Ph 4 P) [V 2 (-OMe) 3 (PS3 00 ) 2 ]Á2MeOH, (I).…”

Redox Interconversion of Non-Oxido Vanadium Complexes Accompanied by Acid–Base Chemistry of Thiol and Thiolate

“…In general, the 51 V nucleus is more deshielded in complexes with S donors than those with N/O ones due to the increasing polarizability . For instance, complexes 3 , 4 , and [V V 2­(PS3″)­2­(μ-E2)­(μ-E)] (1027 and 765 ppm for E = Se and S, respectively) have more downfield 51 V shifts than N/O ligated oxidized amavadin analogues (approximately −200 to −300 ppm). , In addition, the noninnocent nature of ligands such as catecholates also tunes 51 V nucleus in a deshielded manner . The PS3″ ligand in complexes 3 and 4 has a noninnocent character that might also give rise to low shielding.…”

Vanadium O-Centered Selenoiodide Complex: Synthesis and Structure of V4O(Se2)4I6·I2

“…The coordination environment of vanadium atoms (2I + O + 4Se) represents a distorted pentagonal bipyramid (Figure c). For vanadium cations, coordination number 7 may be found both for mononuclear vanadium complexes and a binuclear complex …”

“…For vanadium cations, coordination number 7 may be found both for mononuclear vanadium complexes 4041 and a binuclear complex. 42 Complexes V 4 O(Se 2 ) 4 I 6 are aligned in columns along with direction c. In each column, the neighboring complexes alternate between their two spatial orientations due to rotation via 4 2 axis (Figure 3). Disordered I 2 molecules are situated in the space between the columns.…”