Xinjian Lei

Syntheses, properties and X-ray crystal structures of hexanuclear cobalt-chalcogen clusters Co6S8(PPh3)6 and Co6Se8(PPh3)6·THF

Abstract The reaction of Na2Xx (X = S or Se) with CoBr2 and triphenylphosphine in DMF gave rise to the clusters Co6X8(PPh3)6 [X = S (I), X = Se (II)] in high yields. The molecular structures of I and II have been determined by single-crystal X-ray diffraction. Both structures were solved by direct methods and refined by full-matrix least-squares techniques to converge with R = 0.053 for I and 0.048 for II on the basis of 5488 and 8175 reflections with I > 3σ(I), respectively. The two clusters are isostructural with the inner core consisting of a slightly distorted Co6 octahedron. The CoCo distances fall in the ranges of 2.848–2.894 A for I and 2.955–3.037 A for II. Electrochemistry in dichloromethane shows the electron-transfer sequence for I: Co6S8(PPh3)6⇌[Co6S8(PPh3)6]+ and for II: Co6Se8(PPh3)6⇌[CO6Se8(PPh3)6]+⇌[Co6Se8 (PPh3)6]2+.

Syntheses and Crystal Structures of Two Thiolato-Organophosphino Cobalt(II) Complexes, (Et4N)[Co(SC6H5)3(PPh3)] and [Co(S-m-C6H4CH3)2(Ph2PCH2CH2P(Ph)CH2CH2PPh2)]

Abstract (Et4N)[Co(SC6H5)3(PPh3)] (1) and the neutral complex [Co(S-m-C6H4CH3)2(Ph2PCH2CH2P(Ph)-CH2CH2PPh2)] (2) have been prepared by reaction of CoCl2, NaSR (R = C6H5, m-C6H4CH3) and an organophosphine PPh3, dppep) in methanol. Red crystals of compound 1 are triclinic, space group P 1 with cell dimensions a= 11.284(5), b = 11.987(5), c = 15.929(5) A, α = 91.33(3), β = 96.51(2), γ = 105.42(4)[ddot], Z = 2, Dc = 1.255 g cm−3, R = 0.063 for 1905 observed reflections. The CoPS3 core possesses a distorted trigonal pyramidal geometry. Average distances (Co-S) are 2.262 A and (Co-P) 2.366(2) A. Black crystals of compound 2 are monoclinic, space group P21/c with cell dimensions a = 11.024(3), b = 28.061(2), c = 14.895(2) A, β = 104.59(1)[ddot], Z = 4, Dc = 1.263 g cm−3, R = 0.071 for 2021 reflections. The CoP3S2 core of 2 forms a trigonal bipyramid with average (Co-S) distances of 2.247 A and (Co-P) of 2.241 A.

Syntheses, reactions and spectroscopic properties of Mo(W)CuS cluster compounds, and crystal structure of (Et4N)4[WS4Cu10Br12]

The synthetic reactions and spectroscopic studies of molybdenum(tungsten)-copper-sulfur cluster compounds, which can be prepared by the stepwise or unit construction reactions through the successive addition of CuL (L = Cl, Br, R 2 dtc) across six edges or four faces of MS 4 (M = Mo, W) tetrahedra, are described. A series of Mo(W)CuS cluster compounds, (Et 4 N) 2 [MoCu 2 S 4 (S 2 CNEt 2 ) 2 ] ( 1 ) (Et 4 N) 2 - [MoCu 2 S 3 O(S 2 CNC 4 H 8 ) 2 ( 2 ), [MoCu 2 S 4 (dppe) 2 ] ( 3 ) (dppe = bis(diphenylphosphine ethane, (Et 4 N) 2 [MoCu 3 S 4 (S 2 CNEt 2 ) 3 ] ( 4 ), (Et 4 N) 2 [Mo 2 Cu 4 S 8 (S 2 CNEt 2 ) 2 ] ( 5 ), (Et 4 N) 2 [Mo 2 Cu 4 S 6 O 2 (S 2 CNC 4 H 8 ) 2 ] ( 6 ), [Mo 2 Cu 4 S 8 (dppm) 2 ] ( 7 ), [Mo 2 Cu 4 S 6 O 2 (dppm) 2 ] ( 8 ) (dppm = bis(diphenylphosphine)methane), (Et 4 N) 4 [MoS 4 Cu 10 Br 12 ] ( 9 ), (Et 4 N) 4 [WS 4 Cu 10 Br 12 ] ( 10 ), have been prepared and characterized by IR and 95 Mo NMR spectra. The polynuclear WCu cluster compound (Et 4 N) 4 [WS 4 Cu 10 Br 12 ] ( 10 ) is characterized by single crystal X-ray diffraction analysis. The anion structure consists of a central WS 4 moiety, an octahedral Cu 6 and a tetrahedral Cu 4 array. The average WCu and WS distances are 2.726(8) and 2.247(7) A and the average angles of SWS, SCuS and SCuBr are 109.5(3), 104.1(4) and 112.6(3)°, respectively.

Syntheses and structural characterizations of a series of Mo(W)–Cu–S compounds of bidentate dialkyldithiocarbamate ligands. Crystal structure of [NEt4]2[Mo2Cu5S6O2(Me2NCS2)3]

The complex [NEt4]2[Mo2Cu5S6O2(Me2NCS2)3] has been prepared by the reaction of CuCl, Na[S2CNMe2],NEt4Br, and [NH4]2[MoS2O2] in dimethylformamide solution. It crystallizes in the orthogonal space group Pnma with a= 23.373(3), b= 17.202(3), c= 12.474(4)A, and Z= 4. The Mo2Cu5S6O2 framework in the anion consists of two defective cubane-like units OMoS3Cu2 and OMoS3Cu3 linked through two weak Cu–S bonds and bridged by two Me2NCS2 ligands. The synthesis of the series of compounds [NEt4]2[M2Cu5S8(Me2NCS2)3], [PPh4]2[M2Cu5S6O2(Et2NCS2)3](M = Mo or W), and [NEt4]2[MoCu3S4(Et2NCS2)3] are reported. Their structures are discussed together with their 1H, 13C, and 95Mo n.m.r. spectra in solution.

A low-valence cobalt cluster formed via capture of sulphur atom from ethanedithiol - synthesis and crystal structure of [Co7(μ4-S)3(μ3-S)3(PPh3)6Br] · CH3OH

Abstract The low-valence cobalt cluster [Co 7 (μ 4 -S) 3 (μ 3 -S) 3 (PPh 3 ) 6 Br] ( 1 ) was isolated from the reaction of Co(PPh 3 ) 3 Br with Na 2 edt in ethylene chloride. The skeleton [Co 7 S 6 ] + of 1 can be represented as a monocapped-prismane formed by the addition of the capping atom cobalt to the prismane [Co 6 S 6 ] as shown by X-ray single-crystal structure analysis. In this reaction the S 2− ion is derived from the edt 2− ion through cleavage of the CS bond, and incorporated into the building process.

Condensation of SCH2CH2S2− during the formation of a nickel(II) complex containing mixed ligands. Synthesis and crystal structure of Ni(PPh3p(tpdt)

Reaction of NiCl 2 , PPh 3 and Na 2 edt (edt 2− =SCH 2 CH 2 S 2− ) in methanol gives rise to the cleavage of the C-S bond in edt and a new nickel(II) complex, Ni(PPh 3 )(tpdt)(tpdt 2− =SCH 2 CH 2 SCH 2 CH 2 S 2− ). The complex crystallizes in the monoclinc space group P2 1 /n with a=9.383(4), b=16.380(4), c=14.177(4) A, β=102.75(3) ° ), V=2125.2 A 3 , Z=4; M r =473.30; D c =1.479 gcm −3 ; F(000)=984; μ=12.79 cm −1 . Final R is 0.052 for 2017 observed reflections. The nickel atom is four-coordinated with a distorted square-planar geometry with Ni-S distances in the range 2.150-2.180 A and with Ni-P equal to 2.187 A

Synthesis, structure, and properties of tetraethylammonium bis[bis(2-oxyphenyl)-disulfide-O,O',S] manganese(III)

Abstract The title compound (Et4N)[Mn(MP-MP)2] (1) was obtained by air oxidation of an acetonitrile solution of MnCl2-4H2O and Na2MP. The structure of 1 was determined by single crystal X-ray diffraction methods. Crystal data: C32H36MnNO4S4, monoclinic, P21/c, a = 9.598(3), b = 16.845(3), c = 10.702(3) A, β = 111.20(1)°, V= 1613.1 A3, Z = 2; Mr = 681.84; d x = 1.40g cm−3 F(000) = 712; μ = 6.8cm−1, crystal dimensions 0.40 × 0.20 × 0.20 mm3. The Mn atom is octahedrally and symmetrically coordinated by two MP-MP2- ligands, each providing two phenolate-oxygen and one disulfide-sulfur atoms to form a terdentate. The presence of an S-S bond is revealed by the distance of 2.093 A, which constitutes the first disulphide chelated to the Mn(III) ion. The paramagnetic nature of the high spin Mn(d4) ion is reflected in a value of μcff of 4.83 μB and broad 1H NMR absorptions at 23 ∼ 25ppm and –12∼-17ppm.

Synthesis and crystal structure of a square planar tetra-cobalt complex with two quadruply-bridging sulphur atoms [(η5-Cp)4Co4(µ4-S)2]

The cluster compound [(η5-Cp)4CO4(η4-S)2] was isolated from the reaction between [(η5-Cp)Co(PR3)2] and Li2S at 60 ·C; the tetramer is capped by two quadruply-bridging sulphur atoms above and below the Co4 square plane to form a distorted octahedral core Co4S2 as shown by X-ray single crystal structural analysis.

Coordination behaviour of an unsymmetrical dithiolate with transition metals. Syntheses and properties of propane-1,2-dithiolate complexes and structures of [Ph4As]2[Mn2(1,2-pdt)4] and [Ph4P]2[Ni3(1,2-pdt)4]·2MeCN

SummaryCompounds (C)2[Mn2(1,2-pdt)4], where C = Ph4As+ (1a) or Et4N+ (1b), (Et4N)2[Fe2(1,2-pdt)4] (2) and (Ph4P)2[Ni3(1,2-pdt)4]·2MeCN (3), where 1,2-pdt = propane-1,2-dithiolate, were prepared by reaction of disodium 1,2-propanedithiolate with metal chlorides. Compound (1a) crystallizes in the orthorhombic space group Pbca with a = 10.854(2), b = 22.562(4), c = 24.545(6) Å, V = 6010.8 Å3, Z = 4. The structure was solved from 3003 reflections with I≥3σ(I) and refined to R(Rw) = 0.038(0.045). The two identical fragments [Mn(1,2-pdt)2]− dimerize by bridging through sulfur atoms, on from each of the monomers, to form a rectangular Mn2(μ-S)2 unit. Compound (3) crystallizes in the monoclinic space group P21/c with a = 10.802(2), b = 30.111(7), c = 9.907(3) Å, β = 93.60(3)°, V = 3216.0 Å3, Z = 2. The structure was refined to R(Rw) = 0.063(0.068) from 2256 reflection with I≥3σ(I). The anion of (3) is formed by chelation of two [Ni(1,2-pdt)2]2− units to a central NiII atom. The three NiS4 planes form a chair with a crystallographic centre of symmetry. Complexes (1) and (2) are paramagnetic and dissociate into monomers in solution while (3) is diamagnetic and may not dissociate. Solid state magnetic susceptibility measurements showed the ground state spins of the MnIII and FeIII ions in (1) and (2) to be S = 2 and S = 3/2, respectively, and the two metal atoms in both molecules exhibit antiferromagnetic interactions. The unsymmetrical 1,2-pdt2− ligand chelates to the metal such that the methyl substituent on the terminal carbon atom is remote from the bridging sulfur.

Structure of [bis(2-diphenylphosphinoethyl)phenylphosphine-P,P,P]carbonyl(phenylthiolato)cobalt(I), [Co{Ph2PCH2CH2P(Ph)CH2CH2PPh2}(SPh)(CO)]

[Co(C 34 H 33 P 3 )(C 6 H 5 S)(CO)], P2 1 , a=11.163, b=15.499, c=10.427 A, β=94;18 °, R=0.043.