Search

Tris[o-mercaptophenolato]vanadium(IV) dimer complexes (A)2[V(mp)3NaLL']2 (A = Ph4P+, H2mp = o-mercaptophenol, L = MeCN, L'=EtOH, (1); L' = MeOH, (2)) were prepared by the reaction of anhydrous VC13, and Na2mp in the molar ratio 1:3. Complex (3) (A = Et4N+, L=L' = MeOH) was prepared by the reaction of VC13, Na2mp and Li2S in the molar ratio 1:2:1. The complexes were characterized by X-ray diffraction crystallography, infrared spectra, magnetic susceptibility, and cyclic voltammetric measurements. Complex 2 crystallizes in the triclinic space group P1 with a=12.813(6), b = 14.199(4), c = 12.790(5) A, α = 112.72(2), β = 104.24(4). γ = 88.68(4)°, V = 2073.6 A3, and Z=1. The structure was refined to R=0.058. Complex 3 crystallizes in the mono-clinic space group P21/n with a=12.359(3), b=17.452(6), c=14.829(13) A, βequals;96.51(5)°, V=3177.8 A3, and Z=2. The final R factor is 0.067. Both of the anions of 2 and 3 contain two [V(mp)3]2− fragments linked by sodium ions through the μ3-O bridges with a crystallographic center of symmetry. The V(IV) atom is in a coordination environment intermediate between a trigonal prism and an ideal octahedron.

[Co3(1,2-S2C6H4)3(PPh3)3][CoBr3(DMF)]sol (1, sol=CHCl3·O(C2H5)2·H2O) was obtained from the reaction of CoBr(PPh3)3 with Na2(S2C6H4) in chloroform. The Co3 core in the cation of 1 exhibits a metal-metal bonded isosceles triangle, in which the two longer Co—Co bonds are both bridged by S2C6H4 ligands on two sides of the triangle plane respectively, while the bottom short Co—Co bond is bridged by the third bidentate S2C6H4 ligand. A series of polynuclear cobalt cluster compounds with phosphine, thiolate and/or sulphur ligands were prepared by low oxidation state Co+ with thiolates in organic solvents. These tri-, tetra-, hexa-, heptanuclear cluster compounds 1–8 with various types of crystal structures can be viewed as the condensed polynuclear cobalt complexes that the cobalt atom frameworks with sulphur bridged were built through the small triangular units of [Co3S3nL3] (n=1,2) with or without [CoL] (L=PR3, Br, Cl,5-C5H5) fragments.

A nickel(II) complex containing both dithiolato and phosphine ligands, Ni2(PPh3)2(edt)2 (edt = SCH2CH2S2-), has been prepared and characterized by X-ray diffration. The complex crystallizes in the triclinic system, space group P-1, with a = 10.693(3), b = 17.457 (6), c = 10.606 (3) A, α = 102.84(2), β = 96.49 (2), γ = 82.56(3); V = 1906.8 A3; Dc = 1.439 g·cm−3 for Z = 2; the final conventional R was 0.052 based on 3338 observed reflections. Nickel atoms are linked by two sulfur atoms from two edt ligands with the Ni—Ni distance of 2.893 A, and each Ni atom is coordinated by one phosphorus atom and three sulfur atoms with a square-planar geometry, where the average length of Ni—S bond is 2.180 A and Ni—P bond 2.188 A. The UV-Vis and 1H NMR spectra have also been recorded.

The compound (n-Bu4N)2[W2Cu4S8(S2CNC4H8)2] was obtained by the reaction of Bu4NBr, (NH4)2WS4, NaS2NCC4H8 and CuCl in CH3CN and CH3OH. It crystallizes in the monoclinic space group P21/c with unit cell parameters: a=21.875(5), b=16.843(4), c=17.745(5)A, β = 101.69(6)°, V=6402(6)A3, Z=4, Dc=1.718 g·cm−3. The final R and Rw values converged to 0.055 and 0.060 respectively. The structure consists of two ‘butterfly’ units [WS4Cu2] linked together by two weak Cu—S bonds and two bridging S2CNC4H8 ligands. Infrared spectra gave characteristic absorptions at 495 cm−1 for W=S and 450, 435, 412 cm−1 for W—μ-S.

[V2(μ-S2)2(S2CNEt2)4] 2CH3Cl was synthesized by the reaction of NaS2CNEt2, Li2S and VOCl3 at room temperature. Crystal data: M= 1061.3, space group Pbca, with the orthorhombic parameters: a=20.123(3), b = 20.485(4)1c=10.911(3)A, V=4497.7A3, Z=4, Dc=1.57 g/cm3, Mo Ko radiation (λ=0.71069 A), μ = 13.2 cm−1, F(000)—2168. Final R = 0.041 and Rw=0.047 for 2288 observed reflections with I>3σ(I). The coordination sphere of each V atom in title compound is a distorted tetragonal prism composed of two bidentate dithiocarbamate and two S21− ligands. The V—V distance is 2.890 A while the V—S distances fall in the range of 2.422–2.505 A.

Co4(μ3-S)8(Ph2PCH2sP(O)Ph2)6, MW = 3012.5, space group R3, has the hexagonal parameters, a = 26.764 (10), c = 16.979 (10) A, V = 10532.8 A3, Z = 3. Mo Ka radiation, λ = 0.71069 A, Dc = 1.425 g/cm3, μ = 9.94 cm−3, F(000) = 4650, R = 0.073 and Rw = 0.077 for 1965 observed unique reflections with I > 3σ (I). The molecular structure consists of a distorted octahedral Co4—core. The Co—Co and Co—S distances fall in the range of 2.805—2.838 and 2.213—2.253 A, respectively.

Dendritic metal chalcogenide (HgS, CdS and PbS) single crystals have been prepared via facile and mild solvothermal process in water or ethanol/water systems. SEM and TEM observations show that HgS and CdS dendrites exhibit whole or part of the two-dimensional (2D) hexagonal snowflake spatial pattern while PbS exhibits whole or part of the three-dimensional (3D) octahedral star-like morphology. Selected area electron diffusion (SAED) and HRTEM show that all of these dendrites are single crystals whose shape evolution is closely related to their intrinsic crystal symmetries. The factors influencing the evolution of the crystal morphology, i.e. reactant molar ratio, solvent, sulfur source, reaction time and temperature have been investigated. Two dimensional six-fold symmetrical HgS and CdS dentrites and 3D four-fold symmetrical PbS dentrite have been fabricated by a facile solvothermal method. The crystal evolution process has been investigated.

The self assembly of AgX with the sulfur-containing multidentate ligand α,α′-bis(8-thioquinoline)-m-xylene (m-XYTQ) affords two isomorphous complexes [Ag(m-XYTQ)]nXn (X=ClO4 1; X=BF4 2). Single crystal X-ray analyses revealed the complexes to contain linear cationic chains of [Ag(m-XYTQ)]nn+ in helical arrangement and the anions are discrete. Intramolecular π⋯π stackings pack the asymmetric units [Ag(m-XYTQ)] in shelves-like arrays while interchain π⋯π interactions between racemic chains constructed the 2D network. The key to helix formation is the folding at the sulfur sites of the spacer xylylene in the ligand. The complexes were also characterized by 1H NMR and IR.

The trans-oxamidato dicopper(II) "synthons", [Cu 2 (trans-L)] 2+ (L= oxen, oxpn, oxap, and oxpy) have been used as construction units when further connected by a second bridging ligand L′ (spacer) to fabricate supramolecular architectures via covalent and hydrogen bonding interactions. The structural topologies of the polymeric networks contained by these compounds depend mainly on the coordination modes of the spacers. When the spacers are 2-connectors bridging two synthons, the resulting compounds usually contain 1-D infinite chains, while 3- or 4-connector provides compounds containing 2-D extended coordination networks. The hydrogen bonds, in which the oxamidate, the spacer, and the water molecules are involved, are prevalent and the predominant intermolecular interactions. Compared with the polymeric networks constructed via covalent bonding interactions between synthons and spacers, the structural topologies of the 3-D supramolecular architectures fabricated via hydrogen bonding interactions are mor...

Copper(II) complexes [Cu(acactn)H2O]2 (1) and [Cu2(acactn)2KClO4]2 (2), where H2acactn is a tetradentate Schiff base bis(acetylacetone)trimethylenediimine, have been prepared and characterized by IR, CV and X-ray single crystal structure analyses. The ligand H2acactn is strongly metallophilic to stabilize Cu(II) ion with a square planar N2O2 coordination environment. Complex 1 can be seen as a hydrogen-bonded dimer of building block Cu(acactn) via bridging water molecules, while complex 2 is a tetrametric adduct of [Cu(acactn)] moiety and KClO4, in which K+ and ClO4− are the bridging-groups. Electrochemical studies displayed that Cu(II)/Cu(I) is an irreversible one-electron reduction process.

The flexible multidentate ligand O,O′-bis(8-quinolyl)-1,8-dioxaoctane (ODOQ) reacted with AgX (X = ClO4−, BF4−, CF3SO3−, or CF3CO2−) to give four new complexes [Ag(ODOQ)]nXn: X = ClO4−1; X = BF4−2; X = CF3SO3−3, and [Ag(ODOQ)(CF3CO2)]n4. All four complexes have been characterized by elemental analyses, IR and 1H NMR spectroscopy. Single crystal X-ray analyses showed that they have similar 1-D extended architectures with each ligand in “∼” shape, while the chains are alternately and parallelly arranged with the silver(I) atoms as the backbone to form double helical mesomeric strands. The structures are controlled more by the spacer (CH2)6 than by the anions: the versatile coordination geometry of the silver(I) atom is trigonally bonded but changes to distorted tetrahedral or trigonal bipyrimidal via weak Ag⋯O interactions. In addition, face-to-face π⋯π (in 1–4) and edge-to-face C–H⋯π (in 3) interactions as well as hydrogen bonds C–H⋯O and C–H⋯F between adjacent strands assemble the cations in 1–3 or neutral molecules in 4 into an extended network.

A new ligand 4,5-diazafluorene-9-one benzoylhydrazone (HL) and six of its transition metal complexes ML2·nH2O [ M(II) = Mn, n=2, 1; Co, 2, 2; Ni, 2, 3; Cu, 3, 4; Zn, 1.5, 5; Pb, 4, 6] have been prepared and characterized. Elemental analyses, IR, UV–Vis, 1H NMR, molar conductivity and thermal analyses measurements showed that the ligand coordinates to the metal ion with the enolic O and azomethine N atoms of the acylhydrazone group while the 4,5-diazafluorene moiety is free. Single crystal X-ray diffraction studies showed that CoL2(H2O)2, 2, has a centrosymmetric octahedral geometry of N2O4 with the two bidentate ligands in the basal plane and the two water molecules in the axial sites. The molecules of 2 are linked together by intermolecular hydrogen bonds Ndiazafluorene⋯HOH⋯N′diazafluorene and π–π stacking interactions between the diazafluorene rings to form 2D sheets.

Transition metal complexes M(HL)2·nH2O (M(II)=Mn, n=2 (1); Co, n=3 (2); Ni, n=4 (3); Cu, n=3 (4); Zn, n=2 (5); Pb, n=0 (6)) of 4,5-diazafluorene-9-one salicyloylhydrazone (H2L), have been prepared by the reaction of H2L with the metal(II) acetates in EtOH–DMF. X-ray diffraction studies showed that the ligand in the solid state has a pseudo-helical structure in the keto-form. In complexes Mn(HL)2(H2O)2 (1) and Co(HL)2(DMF)2 (2a), the ligand coordinates to the metal ion as a mononegative ion in the enol-form with the enolic oxygen and azomethine nitrogen atoms of the aroylhydrazone group forming a five-membered chelate ring, while the phenolic hydroxyl group and pyridyl-N atoms of the diazafluorene moiety are free. The metal atoms are in octahedral geometry with N2O4 from two ligands HL in the equatorial plane and the axial sites occupied by solvent molecules. The structures were also characterized by IR and 1H NMR spectroscopy.

New nickel(II) and cobalt(II) complexes of a symmetric acyclic mixed O,N,S-donor ligand, S,S′-bis(8-quinolyl)-4-oxo-1,7-dithiaheptane (OESQ), with quinoline as the terminal group, [M(OESQ)(H2O)](NO3)2 [M = NiII (1) and CoII (2)], have been prepared and characterized by elemental analyses, u.v.–vis. and i.r. spectra, and by magnetic susceptibility measurement. Single X-ray diffraction analyses show that (1) and (2) are isomorphous. The nickel (or cobalt) ion in (1) [or (2)] is hexa-coordinated and the complex cation exhibits a slightly distorted-octahedral geometry defined by all five donor atoms of the ON2S2 of OESQ and a water, molecule with N2S2 in equatorial and two oxygens in axial position.

The reaction of M2+ (M=Co or Ni) with K2(i-mnt) and phosphine forms chelated ternary coordination compounds (1)-(4). The crystal structures of Ni(i-mnt)(dppmSe) (1) (in the presence of Se) and (“Bu4N”)[Co(i-mnt)2(PBu n 2] (2) were determined by single-crystal X-ray diffraction analyses; (1) crystallizes in the monoclinic space group P21/n with a = 12.002(3), b = 19.568(11), c = 12.456(5) A, β = 92.22(3)°, V = 2923.4 A3, Z=2, R(Rw ) = 0.051 (0.062). The distorted, square planar Ni atom forms two individual chelate rings with the two bidentate ligands. Complex (2) crystallizes in space group P 1 with a = 10.682(2), b = 28.496(6), c = 9.959(2) A, α = 91.31(2), β = 97.71(2), γ = 83.68(2)°, V=2986(1)A3, Z=2, R (Rw ) = 0.060 (0.072). The octahedral Co(III) ion in (2) has an elongated structure with two monodentatc phosphines in axial positions and i-mnt groups chelating in the equatorial plane. Spectroscopic characterization was performed where appropriate.

The mononuclear complex (BzMe3N)2[V(mp)3] · MeCN · 1/2 MeOH (1) (mp = o-SC6H4O2−) obtained by reacting VCl3 with Na2mp in the presence of BzMe3NBr contains the synthon [V(mp)3]2−. Further reaction with Co2(CO)8 gave [V(mp)3Co(Py)2(MeCN)] · 2MeCN (2) and [V(mp)3Co(DMF)3] (3), depending on the recrystallization conditions. The coordination geometry of the V atoms in all these complexes lies between an octahedron and a trigonal prism. Upon formation of (2) and (3), the terminal oxo atoms of mp become μ2-O bridges between V and Co, while the latter atom is also octahedral.

Two new members of the hexanuclear series [Co6S8(PR3)6] n+, complexes [Co6S8(PMe2Ph)6](ClO4) (1) and [Co6S8P(OMe)3 6] (2), have been synthesizes and characterized by X-ray diffraction analyses. Their formation process was postulated to go through trinuclear μ3--S bridged moieties. The structural characteristics of the M6E8P6 skeleton of a whole series of [M6E8(PR3)6] n+ (M=Co, Cr, Fe, Mo; E=S, Se, Te) complexes are presented in terms of atomic distances and core volumes.

The reaction of Cp2TiCl2 with o-mercaptophenolate in the presence of a base (Et3N or NaOMe) afforded the complex (BnMe3N)2[Ti(o-SC6H4O)3] or (Et4N)2[Ti2(o-SC6H4O)4(OMe)2]·2H2O under slightly varied conditions. Single-crystal X-ray diffraction studies showed that the Ti(IV) geometry in both complexes is a severely distorted octahedron with average trans-angles of 162.2° and 159.1(2)°, respectively. Crystallographic data for (BnMe3N)2[Ti(o-SC6H4O)3]: a = 9.884(3), b = 16.501(7), c = 23.028(7) A; β = 99.89(3)°, V = 3700.2(22) A3, Z = 4, final R = 0.050 for 3134 observed reflections; for (Et4N)2[Ti2(o-SC6H4O)4(OMe)2]·2H2O: a = 8.953(4), b = 10.148(3), c = 14.527(3) A; α = 73.16(2)°, β = 73.00(3)°, γ = 83.56(4)°, V = 1207.4(9) A3, Z = 1, final R = 0.082 for 2233 observed reflections. The isolation of (BnMe3N)2[Ti(o-SC6H4O)3] provides strong evidence for the synthon character of [Ti(mp)3]2−, which was previously predicted to be present in the complex (Et4N)2[Ti(mp)3Na(MeOH)2]2. Both electronic and 1H NMR spectr...

Neutral heterotetranuclear complex Co3Fe(mp)4(Hmp)(PBun3)3 2 (PBun3 = tri-n-butylphosphine) of 2-mercaptophenol (H2mp) was synthesized in a molar ratio of CoCl2:FeCl3:H2mp:NaOMe:PBun3 = 0.75:0.25:1:2:1 under anaerobic conditions. It represents partially FeIII-substituted form of the asymmetric mixed-valence tetracobalt complex Co4(mp)4(Hmp)(PBun3)3 (1). 2 crystallizes in the triclinic space group Pl, with a = 12.373(2) A, b = 15.677(3) A, c = 20.571(4) A, α = 93.59(3)° β = 93.45(3)° γ = 112.30(3)°, V = 3669 A3, and Z = 2. The molecule exhibits a cyclic skeleton of Co3FeS4O3 with two doubly μ2-S bridges, one doubly μ2-O bridge, and one singly μ2-O bridge. The four mp2− ligands display two different modes, ObSb-T and OtSb, while the monoanion Hmp− is only terminally chelated to Fe3+ ion in HOtSt fashion (b stands for bridge, t for terminal, and T for trinuclear). The three Co centers are located in approximately square-based pyramidal environments, and the Fe atom in distorted trigonal bipyramidal geometry. Three types of main fragment ions were observed in the FAB mass spectrum of 2. The dissociation of the fragments follows the order: PBun3 first, then Hmp and mp ligands. Moreover, the dissociation of Fe(Hmp) is first, followed by Co(mp) and Co(mp)2, according with the fact that Fe(Hmp) is only loosely bonded. Variable-temperature magnetic susceptibility measurements showed that 2 exhibits weak magnetic exchange interactions.

From the reactions of [Et 4 N] 2 MoSe 4 and M(PPh 3 ) n L(M = Cu, Ag, Au: L = Cl, NO 3 : n = 1−2)in univalent comage metal and an MoSe 4 2 unit, [MoSe 4 (CuPPh 3 )PPh 3 ) 2 ] ( 1 ), [MoSe 4 (AgPPh 3 ) Ag(PPh 3 ) 2 ] ( 2 ), [MoSe 4 (Ag-PPh 3 ) 2 ] ( 3 ), [MoSe 4 (AuPPh 3 ) 2 ] ( 4 ), [MoSe 3 )Set(CuPPh 3 ) 3 Cl] ( 6 ), have been isolated and characterized by 93 Mo NMR, IR and Raman spctra. The 93 Mo chemical shifts are mainly dependent upon the shielding effects from the number of the coinage metal atoms around the Mo atom and the geometric structure of the molecule. The shielding order is Au > Cu > Ag. The crystal structure of 4 has been determined by X-ray single-crystal diffraction analysis. It crystallizes in the triclinic space group P -1 with cell constants a = 9.570(2), b = 10.755(2), c = 19.837(4) A : α = 89.59(3), β = 80.37(3), γ = 68.33(3)° and Z = 2 . The molecule has a linear structure with an average Mo distance of 2.846(2) A.

In the study on the reactivity of tetraselenomolybdate, a DMF solution of [Et4N]2[MoSe4] was found to react with 3 equiv of CuCl in the presence of NaS2CNR2 [R2 = Et2, C5H10, (PhCH2)2, Me2] to give a series of Mo−Cu−Se compounds, [Et4N]2[MoCu3Se4(R2NCS2)3] (R2 = Et2 (1a), C5H10 (1b), (PhCH2)2 (1c)) and [Et4N]2[MoCu4Se4(Me2NCS2)4] (2). Furthermore, the reaction of 2 or [Et4N]2[MoSe4(CuCN)2] with [Et4N]2[Cu(SPh)3] in DMF/MeCN afforded a polynuclear Mo−Cu−Se cluster compound, [Et4N]4[MoCu10Se4(PhS)12] (3). [Et4N]2[MoCu3Se4(Et2NCS2)3] (1a) crystallizes in the orthorhombic space group P212121 with cell dimensions a = 12.949(3) A, b = 13.339(3) A, c = 29.744(6) A, V = 5137.6 A3, and Z = 4. Full anisotropic refinements of the structure led to convergence with a value of R = 0.052 (Rw = 0.055) for 453 variables and 6854 reflections (F > 4.0σ(F)). The [MoCu3Se4(Et2NCS2)3]2- anion in 1a comprises three Et2NCS2Cu fragments linked by a slightly distorted tetrahedral MoSe4 moiety. Compound 2 crystallizes in the orthor...

A novel tetranuclear Mo–Cu–Se cluster compound (Ph 4 P) 2 [MoCu 3 OSe 3 Cl 3 (Py)] (Py=pyridine) has been synthesized by the reaction of (Ph 4 P) 2 [MoSe 4 ], CuCl and pyridine in CH 3 CN. X-ray single crystal diffraction analysis reveals that the anion structure consists of an incomplete cubane-like MoCu 3 Se 3 core. The average Mo–Cu and Mo–Se distances are 2.704(7) and 2.394(2) A and the average angles of Se–Mo–Se, Se–Cu–Se, and Se–Cu–Cl are 109.4(2), 104.5(3), and 112.3(3)°, respectively.

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, R2dtc) across six edges or four faces of MS4 (M = Mo, W) tetrahedra, are described. A series of Mo(W)CuS cluster compounds, (Et4N)2[MoCu2S4(S2CNEt2)2] (1) (Et4N)2- [MoCu2S3O(S2CNC4H8)2 (2), [MoCu2S4(dppe)2] (3) (dppe = bis(diphenylphosphine ethane, (Et4N)2[MoCu3S4(S2CNEt2)3] (4), (Et4N)2[Mo2Cu4S8(S2CNEt2)2] (5), (Et4N)2[Mo2Cu4S6O2(S2CNC4H8)2] (6), [Mo2Cu4S8(dppm)2] (7), [Mo2Cu4S6O2(dppm)2] (8) (dppm = bis(diphenylphosphine)methane), (Et4N)4[MoS4Cu10Br12] (9), (Et4N)4[WS4Cu10Br12] (10), have been prepared and characterized by IR and 95Mo NMR spectra. The polynuclear WCu cluster compound (Et4N)4[WS4Cu10Br12] (10) is characterized by single crystal X-ray diffraction analysis. The anion structure consists of a central WS4 moiety, an octahedral Cu6 and a tetrahedral Cu4 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.

A novel polynuclear cobalt complex [Co 7 Na 2 (1,2-OSC 6 H 4 ) 8 (DMF) 12 ] was obtained from the reaction of CoBr(PPh 3 ) 3 with Na 2 (1,2-OSC 6 H 4 ) (H 2 mp= o -mercaptophenol) in DMF and its crystal structure has been determined by single crystal X-ray diffraction analysis. The molecular structure contains nine layers. The cobalt and sodium atoms are arranged in nearly linear chain configuration and bridged by 1,2-OSC 6 H 4 2− and DMF ligands via their oxygen atoms.

The reaction of [Ag(dppm)(NO 3 ] 2 with sodium phenylacetate and dppm in THF at room temperature gave rise to the silver complexes [Ag(dppm)(O 2 CCH 2 Ph)] 2 ( 1 ) and [Ag 2 (dppm) 3 ](NO 3 ) 2 ( 2 ), respectively. Their crystal structures have been determined by single crystal X-ray diffraction analysis. Complex 1 is binuclear with a silver-silver separation of 3.080 A and bridged by two dppm ligands. The cation in complex 2 possesses a Ag 2 P 6 core with AgAg distance of 2.987 A and the silver atoms are each coordinated by three phosphorus atoms in an ideal trigonal-planar environment. Their IR, Raman, 1 H and 31 P NMR spectroscopic properties are also reported.

Mononuclear cobalt(II) complexes Co(mbt-N)2(PBu3n)2 (1) (Hmbt = 2-mercaptobenzothiazole; PBu3n = tri-n-butyphosphine) and Co(mbt-S, N)2(dppe)·MeCN (2) [dppe = 1, 2-bis(diphenylphosphino) ethane] were synthesized and characterized by X-ray crystallography, IR and EPR spectra, cyclic voltammetric data and magnetic susceptibility measurements. The Co atom in (1) exhibits an approximate square-planar geometry with the heterocyclic N-donors from mbt bonding to the cobalt atom in a monodentate mode. Complex (2) has a distorted octahedral environment of Co with both the exocyclic-S and the hetero-N donors of mbt bound to the cobalt atom in a bidentate chelating mode. The Co atom in both complexes shows spin state of S =3/2 with μeff of 4.25 and 4.40μB for 1 and 2, respectively.

The reaction of CoCl2, RuCl3, Na2(mp), and PBun3 (H2mp = 2-mercaptophenol, PBun3 = tri-n-butylphosphine) in ethanol in the molar ratio of 0.75:0.25:1:1 gave the complex Co6Ru2(mp)10(PBun3)6. The heterooctanuclear complex consists of six cobalt and two ruthenium ions chelated to as well as bridged by the 2-mercaptophenol ligands in a near-dimeric fashion with two μ2-OR groups bridging the two Co3Ru(mp)5(PBun3)3 fragments without a crystallographic center of symmetry. Each fragment is formed by binding two of the Co(mp)2(PBun3) structural units and one Co(mp) species to a central Ru(III) ion through the S donors of the five mp ligands, while the sixth coordination site of the octahedral Ru environment is completed by a phosphine ligand in the axial position. The Co6Ru2 moiety exhibits a zigzag assembly constructed by the μ2-O and μ2-S bridges of the bidentate 2-mercaptophenol ligands in a highly asymmetric fashion. The Co atoms are square pyramidally coordinated with apices that are occupied by the phosphin...

The reaction of AgNO 3 , NaS 2 CNEt 2 and H 2 NPhSH in the presence of (Ph 3 P) 3 CuCl in MeOH gave a polynuclear silver cluster compound, [Ag 11 (μ 5 -S)(μ 4 -S 2 CNEt 2 ) 6 (μ 3 -S 2 CNEt 2 ) 3 ]. A cleavage of the S-C bond and release of S 2 from 2-aminothiophenal occurred in the reaction. The core of Ag 11 S consists of five layers: Ag, 3Ag, 3AgS, 3Ag and Ag. The average Ag-Ag and Ag-S c (S c for core sulfur atom) distances are 3.046 and 2.513 , respectively. Copyright © 1996 Elsevier Science Ltd

By the reactions of Pd 2+ , 1,1-dithiolate [SC 6 H 3 (CH 3 )S 2− , SCH 2 CH 2 S 2− or SCH 2 CH (CH 3 )S 2− ] or thiolate (HOC 6 H 4 S − ) and PR 3 (R = Ph, Et) in MeOH, the complexes [Pd(tdt)(PPh 3 ) 2 ] ( 1 ), [Pd 2 (edt) 2 (PPh 3 ) 2 ] ( 2 ), [Pd 2 (pdt) 2 (PPh 3 ) 2 ] ( 3 ), [Pd 2 (edt) 2 (PEt 3 ) 2 ] ( 4 ), [Pd 2 (pdt) 2 (PEt 3 ) 2 ] ( 5 ), [Pd 2 (Hmp) 2 (PPh 3 ) 2 Cl 2 ] ( 6 ) and [Pd 2 (tdt) 2 (PEt 3 ) 2 ] ( 7 ) (tdt = 1,2-toluenedithiolateedt = 1,2-ethanedithiol, pdt = 1,2-propanedithiol and mp = mercaptophenol) were prepared and analysed by X-ray diffraction. All palladium atoms are tetra-coordinated with distorted square-planar geometry of phosphorus and/or sulfur atoms. The reaction mechanism of Pd 2+ , 1,2-dithiolate and PR 3 (R = Et, Ph) is discussed.

The reaction of [Ph3PAgI]4 with sodium phenylacetate in MeOH and CH2Cl2 at room temperature gave rise to a binuclear silver complex with triphenylphosphine and phenylacetate mixed ligands, [Ph3PAg(O2CCH2Ph)]2. The crystal and molecular structure of the complex has been determined by single crystal X-ray diffraction analysis. The space group is $$P\bar 1$$ witha=9.198(2),b=9.516(2),c=13.842(3) A, α=102.00(3), β=108.34(3), γ=93.58(3)°,Z=1, andDc=1.506 g cm−3. The silver atoms are each coordinated by one phosphorus atom from triphenylphosphine and two oxygen atoms from the carboxylate groups in a T-shape. The complex is further characterized by its IR,1H, and31P NMR spectra.

Simple fragments of transition metal 1,2-bidentate thiolates, the so-called building blocks of the general compositions ML3, ML2, ML, M(O)L2, ML2L′, MLL′, etc. have been proposed to constitute the di-, tri- and tetranuclear complexes concerned in this review. Structureal regularities and characteristics have been discussed and summarized according to the thiolato ligands edt and pdt, bdt and tdt, mp, and mpo, and mpp, respectively.

The title compound, octa-μ 3 -thio-hexakis(triphenylphosphine)-octahedro-hexacobalt-triphenylphosphine-1,2-dichloroethane-water (1/2/2/1), [Co 6 S 8 (C 18 H 15 P) 6 ].2C 18 H 15 P.2C 2 H 4 Cl 2 .H 2 O, was prepared by the reaction of CoCl(PPh 3 ) 3 with Na(mpo) (mpo = 2-mercaptopyridine N-oxide) or NaS t Bu. The molecular structure consists of discrete cluster units interspersed with molecules of free triphenylphosphine and solvent. The neutral cluster contains a slightly distorted Co 6 octahedron with each triangular face symmetrically capped by a μ 3 -S ligand. The molecular structure possesses a crystallographic inversion centre. The average Co-Co, Co-S and Co-P bond distances are 2.87 (6), 2.24(1) and 2.162(7)A, respectively. The hexacobalt sulfide cluster compound was formed via the capture of S atoms from thiolate reactants.

A new compound [Na3Co4(μ3-O)2(mpo)8(DMF)4]Br·2DMF (1) was prepared by reacting CoBr(PPh3)3 and Nampo (mpo = 2-mercaptopyridine-N-oxide), and structurally characterized by X-ray diffraction methods. The title compound crystallizes in the triclinic space group P1 with a = 13.393(7), b = 14.00(1), c = 13.029(4) A, α = 92.29(4), β = 110.56(3), γ = 115.32(4)°, V = 2015(2) A3, Z = 1 and R (Rw) = 0.047 (0.053) for 1820 reflections (I > 3 σ(I)). The complex contains four cobalt atoms in the form of a square plane with indirect metal-metal bonds. Each Co atom is coordinated by two bidentate mpo ligands with StOb-D and StOb-T coordination modes, respectively. Two Co2(mpo)4O groups each bridged by μ3-O in the Na3Co4 core are linked by Na3 through the oxygen atoms of the mpo ligands and the bridging μ3-O atoms to form a dumbbell-like structure. The structure of the symmetric tetracobalt cation [Na3Co4(μ3-O)2(mpo)8(DMF)4]+ possesses a crystallographic inversion center through the Na(1) atom. The relevance of the spectroscopic and magnetic properties to the structure of 1 is also discussed.

The mixed polymeric cobalt compound [Co3(SCH2CH2S)3(PEt3)3]2[Co2Cl4(µ-O2SEt2)2]1 containing two trimers and one dimer was isolated from the reaction of [CoCl(PEt3)3] with disodium ethane-1,2-dithiolate in 1,2-dichloroethane. It is monoclinic and crystallizes in space group P21/n, with a= 12.481(7), b= 15.70(2), c= 25.84(2)A, β= 97.85(5)° and Z= 2 from 2436 reflections with I > 3.50σ(I), final R= 0.062. X-Ray diffraction established that the two cobalt atoms in the dimer are linked via the oxygen atoms of the diethyl sulfone forming the eight-membered Co2O4S2 ring with a crystallographic inversion centre through the whole dimer. The observed cleavage of the dithiolate C–S bond together with the formation of the bridging diethyl sulfone are discussed. In the trimer of 1, the Co3 isosceles triangle is capped by two bidentate SCH2CH2S2– ligands on either side of the plane with the sulfur atoms bridging the two long Co–Co bonds, while the short Co–Co bond is bridged by the third SCH2CH2S2– ligand. Considering the framework of the Co3P3(SCH2CH2S)3 unit only, there is a pseudo mirror-image plane passing through the Co3P3 plane which bisects the C(31)–C(32) bond. The 1H NMR spectrum of compound 1 demonstrates the retention of the solid-state structure of the trinuclear species in chloroform solution.

Simple fragments of transition metal 1,2-bidentate thiolates, the so-called building blocks of the general compositions ML3, ML2, ML, M(O)L2, ML2L′, MLL′, etc. have been proposed to constitute the di-, tri- and tetranuclear complexes concerned in this review. Structureal regularities and characteristics have been discussed and summarized according to the thiolato ligands edt and pdt, bdt and tdt, mp, and mpo, and mpp, respectively.

The trans-oxamidato dicopper(II) "synthons", [Cu 2 (trans-L)] 2+ (L= oxen, oxpn, oxap, and oxpy) have been used as construction units when further connected by a second bridging ligand L′ (spacer) to fabricate supramolecular architectures via covalent and hydrogen bonding interactions. The structural topologies of the polymeric networks contained by these compounds depend mainly on the coordination modes of the spacers. When the spacers are 2-connectors bridging two synthons, the resulting compounds usually contain 1-D infinite chains, while 3- or 4-connector provides compounds containing 2-D extended coordination networks. The hydrogen bonds, in which the oxamidate, the spacer, and the water molecules are involved, are prevalent and the predominant intermolecular interactions. Compared with the polymeric networks constructed via covalent bonding interactions between synthons and spacers, the structural topologies of the 3-D supramolecular architectures fabricated via hydrogen bonding interactions are mor...

Compounds (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) A, V = 6010.8 A3, 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) A, β = 93.60(3)°, V = 3216.0 A3, 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.

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

A sulphur and oxygen alternately bridged polymeric silver (I) complex of S,S'-bis (8-quinolyl)-4-oxa-1,7-dithiaheptane (OETQ), [Ag3(OETQ)(NO3)3]∞, was prepared and its structure was characterized by X-ray crystallography. The 2D brick topological open network of the complex is extended via Ag···O interactions. The NO3− anions interact with Ag atoms in versatile forms to control the crystal packing.

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+.

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.

Three new compounds of 2-mercaptophenolate (mp 2- ), trinuclear (Et 4 N)[V 3 (mp) 6 ] or (Ph 4 P)[V 3 (mp) 6 ] (1b), dimeric (Et 4 N) 2 [Co(mp)(Hmp)] 2 (2), and binuclear (Et 4 N) 2 [Ni 2 (Hmp) 2 ] (3), were synthesized and their structures determined. Compound 1b crystallizes in the triclinic space group P1. Compound 2 crystallizes in the monoclinic space group P2 1 /c. Compound 3 crystallizes in the monoclinic space groupe P2 1 /n

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.

The reaction of Co(PPh3)3Cl and K2S2C=C(CN)2 in a 1:1 molar ratio in MeCN led to S-C bond cleavage of [S2C=C(CN)2]2− and allowed isolation of a pentanuclear cobalt cluster compound [Co5(μ3-S)4{μ-SC=C(CN)2}2(PPh3)4] 1 and an octanuclear cobalt cluster compound with mixed Co(I) and Co(II), (PPh4)[Co8(μ4-S)6Br2Cl2(PPh3)4] 2; the core in 1 is a highly distorted Co5 trigonal bipyramid, while that in 2 is a Co8 cube.

A novel polynuclear Mo−Cu cluster compound (Et4N)4[MoS4Cu10Cl12] has been synthesized by the reaction of (NH4)2[MoS4], Et4NCl, and CuCl in acac/DMSO. The reaction mechanism has been monitored by dynamic 95Mo NMR spectra. X-ray single-crystal diffraction analysis reveals that the anion structure consists of a central MoS4 moiety, an octahedral Cu6 array and a tetrahedral Cu4 array, representing the addition of 10 copper atoms across the six edges and four faces of MoS4 tetrahedron. The average Mo−Cu and Mo−S distances are 2.708(8) and 2.238(7) A, respectively.

The title compound, [Ni(C 6 H 5 S) 2 (C 12 H 27 P) 2 ], was isolated from the reaction of NiCl 2 .6H 2 O, NaSPh and P n Bu 3 in MeOH. The molecule possesses a crystallographic inversion center at the Ni atom which is fourfold coordinated by two P and two S atoms with almost square-planar geometry. The Ni-S and Ni-P distances are 2.217 (2) and 2.245 (2) A, respectively.

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.