Tris(tert-butoxo)silylthiolato-Komplexe des Vanadiums(V, IV, III) / Tris(tert-butoxo)silylthiolato Complexes of Vanadium(V, IV, III)

Preuß, Fritz; Steidel, M.; Exner, R.

doi:10.1515/znb-1990-1204

Cited by 14 publications

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“…The anion has the expected square pyramidal coordination geometry, with the two chelate rings in the cis configuration (Figure ). The same cis configuration is found in the other two structurally characterized oxovanadium(IV) complexes with a O 2 S 2 donor set in the basal plane. , The idealized symmetry of the VO 2 S 2 core is C s , with the mirror plane passing through the apical V−O(3) bond and bisecting the O(1)···O(2) and S(1)···S(2) vectors. The vanadium atom is displaced toward the apical oxygen by 0.638(2) Å from the O 2 S 2 least-squares plane, and the largest deviation from this plane is 0.057(2) Å for O(2).…”

Section: Resultssupporting

confidence: 57%

Vanadium(IV) Complexes with Mixed O,S Donor Ligands. Syntheses, Structures, and Properties of the Anions Tris(2-mercapto-4-methylphenolato)vanadate(IV) and Bis(2-mercaptophenolato)oxovanadate(IV)

Klich

Daniher²,

Challen³

et al. 1996

Inorg. Chem.

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Reaction of VO(acac)(2) with 2-mercaptophenol (mpH(2)) in the presence of triethylamine gives the mononuclear tris complex (Et(3)NH)(2)[V(mp)(3)] (1), in which the vanadyl oxygen has been displaced. An analogous reaction using 2-mercapto-4-methylphenol (mmpH(2)) afforded (Et(3)NH)(PNP)[V(mmp)(3)] (2), which was structurally characterized. 2 crystallizes in the orthorhombic space group Pna2(1 )with unit cell parameters (at -163 degrees C) a = 23.974(7) Å, b = 9.569(4) Å, c = 25.101(6) Å, and Z = 4. The coordination geometry around the vanadium is between octahedral and trigonal prismatic. Reaction of VO(acac)(2 )with the sodium salt of 2-mercaptophenol produces the vanadyl(IV) complex Na(Ph(4)P)[VO(mp)(2)].Et(2)O (3), which crystallizes in the triclinic space group P&onemacr; with unit cell parameters (at -135 degrees C) a = 12.185(4) Å, b = 12.658(4) Å, c = 14.244(4) Å, alpha = 103.19(2) degrees, beta = 100.84(2) degrees, and gamma = 114.17(2) degrees. The unit cell of 3 contains a pair of symmetry-related [VO(mp)(2)](2)(-) units bridged through vanadyl and ligand oxygen atoms by a pair of sodium ions, in addition to two PPh(4)(+) ions. The coordination geometry around the vanadium is square pyramidal, with a V=O bond length of 1.611(5) Å. 1, 2, and 3 are characterized by IR and UV-vis spectroscopies, magnetic susceptibility, EPR spectroscopy, and cyclic voltammetry. 1 and 2 can be oxidized by I(2, )Cp(2)Fe(+), or O(2) to [V(mp)(3)](-) and [V(mmp)(3)](-), respectively, which in turn can be reduced back to the dianions by oxalate ion. These reversible redox processes can be followed by UV-vis spectroscopy.

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Section: Resultssupporting

confidence: 57%

Vanadium(IV) Complexes with Mixed O,S Donor Ligands. Syntheses, Structures, and Properties of the Anions Tris(2-mercapto-4-methylphenolato)vanadate(IV) and Bis(2-mercaptophenolato)oxovanadate(IV)

Klich

Daniher²,

Challen³

et al. 1996

Inorg. Chem.

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“…1). This cis con®guration has been seen in the other four oxovanadium(IV) complexes with an O 2 S 2 donor set which have been structurally characterized (Higes-Rolando et al, 1994;Tsagkalidis et al, 1994;Preuss et al, 1990;Klich et al, 1996;Wen et al, 1998). The V(O 2 S 2 ) core thus displays pseudo-C s symmetry with the ' plane passing through the VÐO3 bond and bisecting the O1ÐO2 and S1ÐS2 vectors.…”

Section: Commentmentioning

confidence: 66%

One-dimensional chains in sodium tetraphenylphosphonium bis(2-mercapto-4-methylphenolato-O,S)oxovanadate(IV)

Challen¹,

McConville²,

Youngs³

2000

Acta Crystallogr C

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The title compound, Na(C 24 H 20 P)[V(C 7 H 6 OS) 2 O], contains oxovanadium(IV) in a square-pyramidal coordination geometry with a basal plane consisting of a cis-S 2 O 2 donor group. The [VO(mmp) 2 ] 2À (mmpH 2 = 2-mercapto-4-methylphenol) units are linked into in®nite chains by the sodium ions. CommentThe controlled linking of discrete molecular building blocks into supramolecular aggregates can be achieved through utilizing a number of different kinds of inter-subunit interactions. For oxovanadium(IV) compounds, solid-state and solution structures have been stabilized by speci®c interactions including (i) V OÐV O linkages (Zheng et al., 1995;Aiello et al., 1997;Sa Â ez-Puche et al., 1998), (ii) hydrogen bonds (Wen et al., 1998), (iii) bridging ligands (Salta et al., 1996) and (iv) alkali or alkaline earth ions functioning in a bridging mode (Garcia-Jaca et al., 1993). We have reported (Klich et al., 1996) the vanadyl(IV) complex Na(Ph 4 P)[VO(mp) 2 ]ÁEt 2 O containing the mixed O,S-donor ligand mp 2À [mpH 2 = 2mercaptophenol, C 6 H 4 (OH)(SH)]. In this solid, a pair of [VO(mp) 2 ] 2À anions are linked together through a pair of sodium ions into a centrosymmetric dimer. Each sodium ion is bonded to two ligand O atoms from one [VO(mp) 2 ] 2À unit and to one ligand O atom plus the vanadyl O atom from the other. In the course of these studies, we also prepared the related compound Na(Ph 4 P)[VO(mmp) 2 ] (mmpH 2 = 2-mercapto-4methylphenol), (I), which crystallized in a structure with anionic [NaVO(mmp) 2 À ] I chains. We report herein upon this structure.The square-pyramidal anion, [VO(mmp) 2 ] 2À , contains an apical O atom with a V O bond length of 1.619 (2) A Ê , and an O 2 S 2 basal plane with the two ®ve-membered VÐOÐCÐCÐ S chelate rings in a cis con®guration (Fig. 1). This cis con®guration has been seen in the other four oxovanadium(IV) complexes with an O 2 S 2 donor set which have been structurally characterized (Higes-Rolando et al., 1994;Tsagkalidis et al., 1994;Preuss et al., 1990; Klich et al., 1996;Wen et al., 1998). The V(O 2 S 2 ) core thus displays pseudo-C s symmetry with the ' plane passing through the VÐO3 bond and bisecting the O1ÐO2 and S1ÐS2 vectors. The V atom is displaced 0.598 (1) A Ê from the O 2 S 2 least-squares plane, giving a slightlȳ atter pyramid than in [VO(mp) 2 ] 2À , where the corresponding displacement is 0.638 A Ê . The VÐS and VÐO basal plane bond lengths average to 2.375 and 1.963 A Ê , respectively, and are very similar to those in [VO(mp) 2 ] 2À (2.365 and 1.959 A Ê , respectively) and the other three VO(OS) 2 complexes. The two ®ve-membered chelate rings are folded about the OÐS vector, with the aromatic rings bending toward the apical O atom and making angles of 24.54 (9) and 12.60 (8) with the O1ÐVÐS1 and O2ÐVÐS2 planes, respectively. While this bending is also observed in the related complexes [VO(mp) 2 ] 2À (Klich et al., 1996) and VO(Hmpp) 2 (Wen et al., 1998), it is more pronounced in the title compound. Figure 1The structure of the [VO(mmp) 2 ] 2À dianion. Displ...

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“…The development of facile routes to V(V)−imide complexes ,, has facilitated the expansion of organometallic chemistry of vanadium(V) complexes. ,− Reactions of the vanadium−imide-based precursors, VCl 3 (NAr) (Ar = Ph, C 6 H 3 -2,6- i Pr 2 ), with R 3 PNSiMe 3 (R = Ph, i Pr, t Bu) resulted in the straightforward syntheses of VCl 2 (NPh)(NPPh 3 ) ( 4 ), VCl 2 (NPh)(NP i Pr 3 ) ( 5 ), VCl 2 (NPh)(NP t Bu 3 ) ( 6 ), VCl 2 (NC 6 H 3 -2,6- i Pr 2 )(NPPh 3 ) ( 7 ), VCl 2 (NC 6 H 3 -2,6- i Pr 2 )(NP i Pr 3 ) ( 8 ), and VCl 2 (NC 6 H 3 -2,6- i Pr 2 )(NP t Bu 3 ) ( 9 ), in relatively good yields ranging from 72% to 84%. In the 31 P{ 1 H} NMR spectra, all of these compounds exhibited a typically broad flat-top resonance with line-widths at half-height (Δν 1/2 ) that varied from 532 to 732 Hz.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of Vanadium(V)−Phosphinimide Complexes

Hawkeswood

Stephan

2003

Inorg. Chem.

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Synthetic routes to vanadium(V)-phosphinimide derivatives are addressed. Initial synthetic efforts afforded the known compound formulated as VCl(2)(NPPh(3))(3) which was crystallographically determined to be the salt [VCl(NPPh(3))(3)]Cl (1). Reactions of the vanadium-imide precursors VCl(3)(NAr) (Ar = Ph, C(6)H(3)-2,6-iPr(2)) with R(3)PNSiMe(3) (R = Ph, iPr, tBu) afforded VCl(2)(NPh)(NPPh(3)) (4), VCl(2)(NPh)(NPiPr(3)) (5), VCl(2)(NPh)(NPtBu(3)) (6), VCl(2)(NC(6)H(3)-2,6-iPr(2))(NPPh(3)) (7), VCl(2)(NC(6)H(3)-2,6-iPr(2))(NPiPr(3)) (8), and VCl(2)(NC(6)H(3)-2,6-iPr(2))(NPtBu(3)) (9) in yields ranging from 72% to 84%. Subsequent alkylation or arylation reactions resulted in VMe(2)(NC(6)H(3)-2,6-iPr(2))(NPtBu(3)) (10), VPh(2)(NPh)(NPtBu(3)) (11), VPh(2)(NC(6)H(3)-2,6-iPr(2))(NPiPr(3)) (12), and VPh(2)(NC(6)H(3)-2,6-iPr(2))(NPtBu(3)) (13) while substitution reactions with Li[N(SiMe(3))(2)] and Li[SBn] gave VCl(N(SiMe(3))(2))(NPh)(NPtBu(3)) (14) and V(SBn)(2)(NC(6)H(3)-2,6-iPr(2))(NPtBu(3)) (15) in yields ranging from 40% to 49% yield. Polarization of the N-P phosphinimide bond and V-N multiple bond character are evidenced by crystallographic data.

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Tris(tert-butoxo)silylthiolato-Komplexe des Vanadiums(V, IV, III) / Tris(tert-butoxo)silylthiolato Complexes of Vanadium(V, IV, III)

Cited by 14 publications

References 0 publications

Vanadium(IV) Complexes with Mixed O,S Donor Ligands. Syntheses, Structures, and Properties of the Anions Tris(2-mercapto-4-methylphenolato)vanadate(IV) and Bis(2-mercaptophenolato)oxovanadate(IV)

Vanadium(IV) Complexes with Mixed O,S Donor Ligands. Syntheses, Structures, and Properties of the Anions Tris(2-mercapto-4-methylphenolato)vanadate(IV) and Bis(2-mercaptophenolato)oxovanadate(IV)

One-dimensional chains in sodium tetraphenylphosphonium bis(2-mercapto-4-methylphenolato-O,S)oxovanadate(IV)

Synthesis and Characterization of Vanadium(V)−Phosphinimide Complexes

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