[Ph4P]2[V2(SC2H4S)4]-4MeOH: Der erste Vandium-Schwefel-Mehrkernkomplex mit reiner Schwefelkoordination

Szeymies, Detlef; Krebs, Bernt; Henkel, Gerald

doi:10.1002/anie.198311760

Cited by 5 publications

(4 citation statements)

References 21 publications

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“…They are in the range of 2.31−2.32 Å, 2.39 Å, and 2.50−2.54 Å, respectively, in agreement with V−S bond distances of reported V(III) thiolate complexes (Supporting Information, Table S2). − The average P−V−S angle of these complexes varies with different geometries (82−84° for 1 − 5 , 79° for 6 , and 72−74° for 7 and 8 ), reflecting the flexibility of PS3 ligand system.…”

Section: Resultsmentioning

confidence: 99%

Family of V(III)-Tristhiolato Complexes Relevant to Functional Models of Vanadium Nitrogenase: Synthesis and Electronic Structure Investigations by Means of High-Frequency and -Field Electron Paramagnetic Resonance Coupled to Quantum Chemical Computations.

Neese

Ozarowski

et al. 2009

Inorg. Chem.

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A series of V(III) complexes of varying coordination number (5, 6, and 7) all containing the PS3 ligand (PS3 = trianion of tris(2-thiophenyl)phosphine and its derivatives with other phenyl substituents) has been prepared and structurally characterized. The complexes have general formula [V(PS3)L(n)](0,-), where n = 1 (from L = Cl(-), 1-Me-Im, N(3)(-)), 2 (from L = 2,2'-bpy; counting each N of the bidentate ligand), and 3 (from L = 1-Me-Im, N(2)H(4)). The complexes have also been investigated by direct current (DC) magnetic susceptibility and high-frequency and -field electron paramagnetic resonance (HFEPR). HFEPR, supported by magnetometry, has provided accurate spin Hamiltonian parameters that describe the S = 1 spin ground state of the complexes. Of particular interest are the zero-field splitting (zfs) parameters which, together with structural data, are the empirical starting point for detailed computational studies. The computational methods included density functional theory (DFT), which was only marginally successful, and more advanced ab initio methods (CASSCF and SORCI). The zfs in these complexes is relatively small in magnitude (|D| approximately 1 cm(-1)) and is the result of multiple, often counteracting, spin-orbit coupling (SOC) and spin-spin coupling (SSC) contributions. The specific origin of each of these contributions is described in detail. The results indicate the level of electronic structure calculation possible for transition metal complexes even with multiple unpaired electrons and highly covalent, heavier atom donor ligands.

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Section: Resultsmentioning

confidence: 99%

Family of V(III)-Tristhiolato Complexes Relevant to Functional Models of Vanadium Nitrogenase: Synthesis and Electronic Structure Investigations by Means of High-Frequency and -Field Electron Paramagnetic Resonance Coupled to Quantum Chemical Computations.

Neese

Ozarowski

et al. 2009

Inorg. Chem.

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“…Addition of excess tht to NbX3S (X = Cl, Br) resulted in a reduction to niobium(III), concomitant oxidation of two sulfide ligands to an S22ligand, and the formation of a diniobium species containing both ju-S and S2 ligands (eq 24).45 An X-ray (24) structure showed that the S22-ligand lies perpendicular to the bioctahedral plane with its midpoint in the plane. This complex was later obtained46 by addition of tht to Nb2X4S3, which is formed in the reaction of Sb2S3 and NbX5 (eq 25); crystals of Nb2X4S3 could not be ob- (25) tained, but these species are also believed to contain S and S2 ligands. A number of other diamagnetic, and thus presumably diniobium(IV), adducts were obtained with SMe2, NCMe, and PhSCH2CH2SPh but were not structurally characterized.…”

Section: Edge-sharing Bioctahedral Complexes With Monodentate Ligandsmentioning

confidence: 99%

Metal-metal bonded dinuclear and organodimetallic complexes of the early transition metals (Groups 4 and 5): synthesis, structure, and reactivity

Messerle¹

1988

Chem. Rev.

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“…Vanadium sulfide complexes are considered to be likely intermediates during hydrodemetalation and hydrodesulfurization in the processing 3 of crude oil. Vanadium chemistry has had an impressive advance [4][5][6][7][8][9][10][11][12][13][14][15][16][17] and is proving sufficiently different from the corresponding Mo chemistry, despite that the former is usually seen as an extension of the latter. Our interest in this area concentrates on the riches of structure types of the V/S(O) complexes and studies on synthetic systems and clustering mechanisms.…”

Section: Introductionmentioning

confidence: 99%

Studies on the Synthetic System of V/Ag/S Cluster Compounds and Structural Characterizations of V₂AgS₄, V₂Ag₂S₄, and V₂O₂(μ-S)₂ Complexes

et al. 1998

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The reaction system (NH(4))(3)VS(4)/Ag(PPh(3))(2)Cl/R(2)dtcNa in CH(3)CN was studied to afford two V(2)Ag(1)(-)(2)S(4) cubanelike cluster compounds and a trinuclear V(3)O(3)S(2) complex. (Et(4)N)[V(2)AgS(4)(Me(2)dtc)(2)(PPh(3))].(1)/(2)CH(3)CN ([Et(4)N]1.(1)/(2)CH(3)CN) crystallizes in the monoclinic space group P2(1)/c with a = 10.525(3) Å, b = 16.340(8) Å, c = 26.834(8) Å, beta = 101.28(2) degrees, and Z = 4. Complex (Et(4)N)(2)[V(2)Ag(2)S(4)(CS(3))(2)(PPh(3))(2)] ([Et(4)N](2)2) crystallizes in the monoclinic space group C2/c with a = 21.212(5) Å, b = 20.100(4) Å, c = 15.039(2) Å, beta = 102.72(2) degrees, and Z = 4. A stepwise aggregate process including a dinuclear V(2)Y(2)(&mgr;-S)(2) (Y = S, O) intermediate was suggested to explain the formation of 1, 2, and trinuclear anion [V(3)O(&mgr;-O)(2)(&mgr;-S)(2)(Et(2)dtc)(3)](-). Structural features of these complexes show that the V(2)Y(2)(&mgr;-S)(2) moiety can be seen as an independent unit to combine with other metal ion(s). A complex containing the [V(2)O(2)(&mgr;-S)(2)(Et(2)dtc)(2)](2)(-) (3) cluster anion was separated from a reaction system of (NH(4))(3)VS(4)/PPh(3)/Et(2)dtcNa, and its solvate complex {(Et(4)N)(3)Na[V(2)O(2)(&mgr;-S)(2)(Et(2)dtc)(2)](2)}(2).(1)/(2)CH(3)OH.H(2)O crystallizes in orthorhombic space group Pnn2 with a = 31.599(1) Å, b = 17.228(5) Å, c = 14.104(7) Å, and Z = 2. Infrared frequencies at 844-970 cm(-1) were associated with a V=O stretching vibration. The V=O additional coordination to the other metal ion gives rise to the red shift of the frequency. Proton and (51)V NMR spectra exhibit a paramagnetic V(IV) center existing in the trinuclear complex (Et(4)N)[V(3)O(&mgr;-O)(2)(&mgr;-S)(2)(Et(2)dtc)(3)] ([Et(4)N]4) and d(1)-d(1) coupling of V-V of the V(2)Y(2)(&mgr;-S)(2) moiety for these complexes. Two sets of the (31)P signals for 2at 16.6-19.3 ppm with equal intensity are attributed to (31)P-(107)Ag coupling and may well hide two V atoms in a similar environment. Cyclic voltammetries show some similar electrochemical behaviors between 3 and 4 indicated by a common couple at -0.7 V/-0.65 V and an oxidation peak at +0.7 to +0.6 V which are proposed to be due to redox in the V(2)O(2)(&mgr;-S)(2) moiety.

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[Ph4P]2[V2(SC2H4S)4]-4MeOH: Der erste Vandium-Schwefel-Mehrkernkomplex mit reiner Schwefelkoordination

Cited by 5 publications

References 21 publications

Family of V(III)-Tristhiolato Complexes Relevant to Functional Models of Vanadium Nitrogenase: Synthesis and Electronic Structure Investigations by Means of High-Frequency and -Field Electron Paramagnetic Resonance Coupled to Quantum Chemical Computations.

Family of V(III)-Tristhiolato Complexes Relevant to Functional Models of Vanadium Nitrogenase: Synthesis and Electronic Structure Investigations by Means of High-Frequency and -Field Electron Paramagnetic Resonance Coupled to Quantum Chemical Computations.

Metal-metal bonded dinuclear and organodimetallic complexes of the early transition metals (Groups 4 and 5): synthesis, structure, and reactivity

Studies on the Synthetic System of V/Ag/S Cluster Compounds and Structural Characterizations of V₂AgS₄, V₂Ag₂S₄, and V₂O₂(μ-S)₂ Complexes

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[Ph4P]2[V2(SC2H4S)4]-4MeOH: Der erste Vandium-Schwefel-Mehrkernkomplex mit reiner Schwefelkoordination

Cited by 5 publications

References 21 publications

Family of V(III)-Tristhiolato Complexes Relevant to Functional Models of Vanadium Nitrogenase: Synthesis and Electronic Structure Investigations by Means of High-Frequency and -Field Electron Paramagnetic Resonance Coupled to Quantum Chemical Computations.

Family of V(III)-Tristhiolato Complexes Relevant to Functional Models of Vanadium Nitrogenase: Synthesis and Electronic Structure Investigations by Means of High-Frequency and -Field Electron Paramagnetic Resonance Coupled to Quantum Chemical Computations.

Metal-metal bonded dinuclear and organodimetallic complexes of the early transition metals (Groups 4 and 5): synthesis, structure, and reactivity

Studies on the Synthetic System of V/Ag/S Cluster Compounds and Structural Characterizations of V2AgS4, V2Ag2S4, and V2O2(μ-S)2 Complexes

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Studies on the Synthetic System of V/Ag/S Cluster Compounds and Structural Characterizations of V₂AgS₄, V₂Ag₂S₄, and V₂O₂(μ-S)₂ Complexes