[Ph₄P]₂[V₂(SC₂H₄S)₄]·4MeOH: The First Polynuclear Vanadium‐Sulfur Complex with Pure Sulfur Coordination

Abstract

Chem. SO3 (1983) 22. 131 Main absorption bands in the IR spectrum (anion vibrations of 3b; CsI pellet): -3580 w (<OH)), 1560 s (<NO)), 810 m <Mo(OH)Mo), 608 m (v(MoN): 6(NO)), 521 m (v(S2)), 474 w/425 m (<S5)), 341/315 m (v(MoS)) cm-'. [4] 3b crystallizes in the space group P2,/n, a=1114.8(4), b= 1588.0(5), c = 1206.7(4) pm, 8=97.09(3), 2 = 4 ; R=0.065 for 2587 independent reflections (Syntex P2,; Mo,,). The single crystal structure analysis of the isostructural complex 3a leads to almost the same structure of the anion 3. IS] Procedure: A mixture of ( N H & M o , O~~.~H~O (2.5 g), NH20H-HCI (2.1 g) and KSCN (15 g) or NHISCN (I5 g) (3a and Jb, resp.) in water (20 mL) is heated with stirring for 1 h at 80°C. To the solution, which contains [Mo(NO)(NH2O)(NCS),l2-121, 55 mL of ammonium polysultide solution is added [obtained by passing HIS (e4. 1.5 H) into a suspen-sion of 9 g sulfur in an aqueous NH3 solution (200 mL 25% solution diluted with 300mL H20)1-for 3a in addition 2 g KH2P04 and 4 g Na2HP04 as buffer-and transferred to a 300 mL Erlenmeyer flask (in all operations covered with a watch glass). The mixture is heated to 50-55°C for Id and then allowed to cool to room temperature. 3a : After 2 weeks the precipitated orange-red crystals obtained as sole reaction product (besides sulfur) are filtered off and washed with ethanol and CS2.(Any precipitate produced after 1 week is filtered off). Yield 1.0g-3b: procedure as for the isostructural compound 38. However, along with the orange-red, lance-shaped crystals 3b (formed at the glass/air/solution contact) also sulfur (as a result of the high NHZ-content and the low pH value of the solution) and NHZ the salt of 2 [lb] separate out at the bottom of the flask. Yield (separated mechanically) 0.1 g. Fig. 1. Structure of the anionic complex 1 in crystals of the salt 2 with vibration ellipsoids (140 K, 50% probability, without H atoms). Selected distances [pm] (u 0.1 pm): V(l)-. -V(2) 257.5; V-(pS):V(l)-S(2) 236.8, V(I)-S(3) V(2)-S(2) 248.0, V(2)-S(3) 249.2; V-(S,erm): V(I)-S(5) 238.4, V(l)-S(6) 238.0, V(2)-S(8) 237.0, V(2)-S(7) 236.6; Range of SVS angles ["I (o 0.05"): V(1) 70.59 to 161.39, V(2) 70.75 to 164.79. Further details of the crystal structure investigation are available on request from the Fachinformationszentrum Energie Physik Mathematik, D-7514 Eggenstein-Leopoldshafen on quoting the depository number CSD 50534, the names of the authors, and full citation of the journal. 239.3, V(1)-S(1) 248.5, V(I)-S(4) 249.3, V(2)-S(I) 237.5, V(2)-S(4) 238.5, nedithiolate ligand. The resulting coordination polyhedron can be derived from an ideal trigonal prism by rotating the S(S)-S(6) edge twofold the around axis on which the vanadium atoms are sited. This is demonstrated in Figure 2, which shows a schematic projection along the V-V axis to the plane of the four bridging sulfur atoms. The S(S)-S(6) edge of the prism is twisted through an angle p from ideal symmetry; for the distorted prisms of the two metal atoms this angle is cu. 30" @v(lJ and 36" (u~(~,), respectively.

Probing Nuclear Spin Effects on Electronic Spin Coherence via EPR Measurements of Vanadium(IV) Complexes

“…Unfortunately, attempts to synthesize [V­(C 3 H 6 ­S 2 ) 3 ] 2– , the analogue of the smallest member of the vanadyl series, were unsuccessful. We hypothesize that this is due to the formation of multinuclear complexes, as was previously observed with reaction of the 1,2-ethane­dithiolate ligand with vanadium­(IV) …”

Magnetochemical Properties and Reactions of Vanadium(III) Thiolate Complexes: Preparation of (NEt4)3[V3Cl6(edt)3] and Mixed-Valence (NEt4)[V2(edt)4] (edt = Ethane-1,2-dithiolate)

“…VCl 3 , NEt 4 Cl, NBu n 4 PF 6 , edtH 2 , thianthrene, and Me 3 SiCl were used as purchased and stored under dinitrogen. (NEt 4 ) 2 [V 2 (edt) 4 ] ( 1 ), VCl 3 (THF) 3 , and (C 12 H 8 S 2 )(BF 4 ) (C 12 H 8 S 2 = thianthrene) were prepared by literature methods. Sodium acenaphthylenide (NaACN) was prepared by dissolving Na metal in a THF solution of acenaphthylene.…”

“…The present report describes an investigation of certain reactivity characteristics of the [V 2 (edt) 4 ] 2- (edtH 2 = ethane-1,2-dithiol) anion. This species was reported many years ago by three separate groups at nearly the same time, and subjected to crystallographic 11 and electrochemical characterization, 10j,11b as well as an extended Hückel theory EHT calculation . We recently became interested in the magnetic properties of this species and also its use as a source of other V complexes, including its one-electron-oxidized form and a new trinuclear complex; we herein describe the results of this work.…”

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

“…A broad resonance at 231 ppm was observed in the 51 V NMR (Figure b) of [Et 4 N] 2 2 , which is believed to be responsible for the V IV (μ-S) 2 V IV moiety with a V−V single bond and may also be an indication of the two V atoms being in a similar environment. A comparable example is [V 2 (S 2 ) 2 (CS 3 ) 4 ], − which shows its sharp 51 V resonance at 125 ppm in DMSO/CD 3 CN. It is obvious that V IV nuclei in complex [Et 4 N] 2 2 are less effectively shielded by five S atoms than those of [V 2 (S 2 ) 2 (CS 3 ) 4 ] 4- shielded by eight S atoms, giving rise to the 51 V signal downfield.…”