Synthesis and Characterization of syn-[(η~5-C_5Me_5)_2W_2(S)_2(μ-S)_2].0.5anti-[(η~5-C_5Me_5)_2W_2(S)_2(μ-S)_2]

1 INTRODUCTION The complexes of syn- or anti-[(5-C5Me5)2- W2(S)2(-S)2] could be prepared in several ways[1~5]. For example, a mixture consisting of [Et3NH][(5-C5Me5)WS3] and anti-[(5-C5Me5)2- W2(S)2(-S)2] was generated from the reactions of [(5-C5Me5)WCl4] with H2S in the presence of NEt3[2]. The reactions of [(5-C5Me5)W(NO)I2] with H2S led a mixture of [(5-C5Me5)W(S)(S2)I] and anti-[(5-C5Me5)2W2(S)2(-S)2][3]. [(5-C5Me5)W- (StBu)3] was degraded in THF at room temperat…     

Synthesis and Structural Characterization of [(η~5-C_5Me_5)_2Mo_2Fe_2S_4Br_2]

1 INTRODUCTION We once reported a CS bond cleavage reaction of (h5-C5Me5)Mo(StBu)3, which led to a Mo(IV) thio/thiolate complex (h5-C5Me5)MoS2(StBu)[1]. This reaction was facilitated by oxidants such as S8, gray selenium, and FeCl3[2]. The reaction with FeCl3 gave rise to a cubane cluster [(h5-C5Me5)2Mo2Fe2S4Cl2], which served as an excellent building block to construct various Mo/Fe/S clusters[2]. In this paper, we report the crystal structure of [(h5-C5Me5)2Mo2Fe…     

Synthesis and characterization of MH···HOR dihydrogen bonded ruthenium and osmium complexes(η~5-C_5H_4CH_2OH)MH(PPh_3)_2(M = Ru,Os)

Treatment of RuCl2(PPh3)3 with 6-dimethylaminopentafulvene in THF in the presence of water produced(η5-C5H4CHO) RuCl(PPh3)2, which was reduced by NaBH4 to give the Ru–H···HO dihydrogen bonded complex(η5-C5H4CH2OH) RuH(PPh3)2. The dihydrogen bonded complex(η5-C5H4CH2OH)RuH(PPh3)2 could also be synthesized by the reduction of complex(η5-C5H4CHO)RuH(PPh3)2, which was obtained by the reaction of RuHCl(PPh3)3 with 6-dimethylaminopentafulvene in the presence of water. The analogous dihydrogen bonded osmium complex(η5-C5H4CH2OH)OsH(PPh3)2 was similarly prepared. Single crystal structures and DFT calculations support the presence of intra-molecular H···H interaction, with separations of around 1.9 to 2.0 .     

[Co_3(1,2-S2C6H4)_3(PPh_3)_3]+, A basic triangle unit of some polynuclear molecules

[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 polynu-clear 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.     

Synthesis and Crystal Structure of an Incomplete Cubane-like Heterobimetallic Cluster [(η~5-C_5Me_5)_2Mo_2(μ_3-S)(μ-S)_3(CuCl)]

The reaction of [(η5-C5Me5)2Mo2(μ3-S)4(CuCl)2] 1 with Na2S in MeCN produced a trinuclear cluster [(η5-C5Me5)2Mo2(μ3-S)(μ-S)3(CuCl)] 2. 2 crystallizes in the monoclinic system, space group P21/c with a = 15.563(3), b = 8.9547(18), c = 17.846(4) , β = 101.29(3)o, V = 2438.9(9) 3, Z = 4, Dc = 1.878 g/cm3, T = 193(2) K, C20H30ClCuMo2S4, Mr = 689.60, F(000) = 1376, μ(MoKα) = 2.335 mm–1, S = 1.050, R = 0.0305 and wR = 0.0688 for 4033 observed reflections with I > 2σ(I). In the structure of 2, one [(η5-C5Me5)2Mo2(μ-S)2S2] moiety and one CuCl unit are assembled into an incomplete cubane-like [Mo2S4Cu] core framework, in which the Cu center adopts a distorted tetrahedral geometry coordinated by one μ3-S atom, two μ-S atoms and one terminal chloride. The two Mo…Cu contacts are 2.7519(7) and 2.7689(8) , respectively.     

Syntheses and Crystal Structures of Two Heterobimetallic Clusters [WOS_3Cu_3I(dmpzm)_2]·2(MeCN)_(0.5) and [WS_4Cu_4I_2(dmpzm)_2]·DMF(dmpzm=Bis(3,5-dimethylpyrazolyl)methane)

The reaction of [Et4N]2WOS3 with three equiv.of CuI and dmpzm in MeCN afforded [WOS3Cu3I(dmpzm)2]·2(MeCN)0.5(1·2(MeCN)0.5) while that of [PPh4]2WS4 with four equiv.of CuI in DMF/MeCN followed by the addition of two equiv.of dmpzm in MeOH gave rise to [WS4Cu4I2(dmpzm)2]·DMF(2·DMF).Both compounds were characterized by elemental analysis,IR,and single-crystal X-ray diffraction analysis.1·2(MeCN)0.5 crystallizes in triclinic,space group P1-with a = 11.4552(5),b = 11.6735(3),c = 16.2278(9) ,α = 99.537(9),β = 101.986(2),γ = 118.464(13)o,V = 1775.5(3)3,Z = 2,μ = 6.080 mm-1,Dc = 1.983 Mg/m3,T = 193(2) K,C24H35Cu3IN9OS3W,Mr = 1063.22,F(000) = 1018,S = 1.060,R = 0.0376 and wR = 0.0870.2·DMF belongs to the orthorhombic system,space group Pmn21 with a = 22.145(4),b = 11.464(2),c = 7.7370(15) ,V = 1964.2(6)3,Z = 2,μ = 6.865 mm-1,Dc = 2.189 Mg/m3,T = 193(2) K,C25H39Cu4I2N9OS4W,Mr = 1301.72,F(000) = 1226,R = 0.0632,wR = 0.1706 and S = 1.130.1·2(MeCN)0.5 consists of one CuI and two [Cu(dmpzm)]+ fragments that are linked by [WOS3]2-species via six Cu-S bonds,forming a nido-like [WS3Cu3] core.2·DMF contains a saddle-shaped [WS4Cu4] core with two iodides coordinated at two Cu centers in a cis position and two dmpzm ligands being chelated at another two Cu centers in a cis position.     

Synthesis and Crystal Structure of an Incomplete Cubane-like Heterobimetallic Cluster [(η5-C5Me5)2Mo2(μ3-S)(μ-S)3(CuCl)]

The reaction of [(η5-C5Me5)2Mo2(μ3-S)4(CuCl)2] 1 with Na2S in MeCN produced a trinuclear cluster [(η5-C5Me5)2Mo2(μ3-S)( μ3-S)3(CuCl)] 2. 2 crystallizes in the monoclinic system, space group P21/c with a=15.563(3), b=8.9547(18), c=17.846(4) (A), β=101.29(3)°, V=2438.9(9) (A)3, Z=4, Dc=1.878 g/cm3, T=193(2) K, C20H30ClCuMo2S4, Mr=689.60, F(000)=1376, μ(MoKα)=2.335 mm–1, S=1.050, R=0.0305 and wR=0.0688 for 4033 observed reflections with Ⅰ ＞ 2σ(Ⅰ). In the structure of 2, one [(η5-C5Me5)2Mo2(μ-S)2S2] moiety and one CuCl unit are assembled into an incomplete cubane-like [Mo2S4Cu] core framework, in which the Cu center adopts a distorted tetrahedral geometry coordinated by oneμ3-S atom, twoμ-S atoms and one terminal chloride. The two Mo…Cu contacts are 2.7519(7) and 2.7689(8) (A), respectively.     

Synthesis and crystal structure of chain [Cu_2I_2(PPh_3)_2(C_4H_5N_3)]∝

The chain [ Cu2I2(PPh3)2(C4H5N3)] has been synthesized and characterized by X-ray crystallography.It crystallizes in the triclinic system,space group P 1,with a=0.9985(2)nm,b=1.0998(2)nm,c=1.5174(2)nm,a=87.89(1),P=76.73(l),7=77.77(1),V=1.5849(5)nm3,Z=2,Bc=2.095g/cm3 [Gu2I2(PPh3)2(Crh5N3)] has a dimmer unit [Cu2I2(PPh3)2(C4H5N3)].The two N atoms of the phenyl ring of 2-aminopyrimidine bridge two [CuI(PPh3)]2 units,by which a one-dimensional chain is constructed.The van der Waals force makes the molecules arrange in the three-dimensional space.     

Synthesis and Thermal Rearrangement of Tetramethyldisilane-bridged Bis(cyclopentadienyl) Diiron Complexes with Bis(phosphine)Substitution

Photolysis of [Me2SiSiMe2)[C5H4Fe(CO2)]2with a series of bis(phosphine)ligands Ph2P(CH2)n PPh2(n=1-4) leads to the formation of the corresponding diiron complexes with intramolecular and intermolecular bis(phosphine) substitution.When these complexes were heated in refluxing xylene.only in the complexes with intermolecular bis(phosphine )substitution the thermal rearrangement reaction occurred.     

环戊二烯基钌配合物催化的高选择性苯乙炔二聚反应

Transition metal vinylidene complexes (M=C=CHR) have attracted a great deal of attention in recent years as a new type of organometallic intermediates that may have unusual reactivity[1]. Their reactivity has been explored and their application to organic synthesis is developed[2]. Recent reports on the ruthenium-vinylidene complexes[3]suggest that the reaction of ruthenium-vinylidene complexes with a base generates the coordinatively unsaturated ruthenium acetylide species, which are involved in a number of catalytic and stoichiometric reactions of alkynes. For example,the coordinatively unsaturated ruthenium acetylide species C5Me5Ru(PPh3)-C≡CPh,formed from the reaction of the vinylidene complex C5Me5Ru(PPh3) (Cl)=C=CHPh with a base was reactive toward a variety of small molecules and active in catalytic dimerization of terminal alkynes[4]. The dimerization of terminal alkyne is an effective method of forming enynes, but its synthetic application in organic synthesis has been limited dueto low selectivity for dimeric products[5]. In this communication, we report that three ruthenium complexes were used as catalysts for the highly selective dimerization of phenylacetylene.     

Synthesis and Crystal Structure of {(PPh3)2ClRu(μ-Cl)-Ru(PPh3)B10H7[OCH(CH3)2]3}·0.4(H2O)

The title compound has been synthesized by the reaction of [RuCl2(PPh3)3] and closo-[B10H10]2- in (CH3)2CHOH solution. Crystals suitable for a single crystal X-ray diffraction analysis were obtained from n-pentane diffused to CH2Cl2 solution. The crystal {(PPh3)2ClRu(μ-Cl)Ru(PPh3)B10H7[OCH(CH3)2]3}·0.4(H2O) is monoclinic , space group P21/n , Mr=1359.47, with a=19.434(4), b =14.340(4), c=25.865(9)(A), β= 95.48(3)°, V=7175(4)(A)3, Dc=1.258 g/cm3, Z=4, λ(MoKα)=0.71073(A),μ=6.03 cm-1, F(000)=2784, R=0.0631, wR2= 0.1425, S=1.001. The title compound is a bimetallic species in which the second ruthenium center is bound to the cluster {(PPh3)RuB10H7[OCH(CH3)2]3} via an Ru-Cl-Ru and two Ru-H-B-Ru bridges. The third isoproxy group replaces a hydrogen atom on B(10) of the cage, which indicates the activity of the cage.     

Syntheses and Structures of Two Ruthenium(Ⅲ) Complexes [Ru(PPh_3)_2(S_2CNR_2)Cl_2]·CH_2Cl_2(R=Et and ~iPr)

Oxidation reaction of [Ru(PPh3)3Cl2] with tetraethylthiuram disulfide [Et2NCS2]2 or tetra-iso-propylthiuram disulfide [iPr2NCS2]2 afforded ruthenium(Ⅲ) complexes [Ru(PPh3)2(S2CNR2) Cl2]·CH2Cl2(R=Et 1,iPr 2) which were characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P with a = 11.5065(6),b = 12.1458(7),c = 18.0034(9) ,α = 109.380(4),β = 95.279(4),γ = 97.969(4)°,V = 2324.8(2) 3 and Z = 2.Complex 2 belongs to the monoclinic system,space group P21/n with a = 12.5752(3),b = 20.7562(5),c = 17.6821(3) ,β = 105.934(1)°,V = 4437.94(17) 3 and Z = 4.Both mononuclear complexes 1 and 2 have an octahedral configuration around the central ruthenium atom which is bonded to one chelated dithiocarbamate ligand,two PPh3 ligands in mutually trans and two chlorides in mutually cis positions.The average Ru-S,Ru-P and Ru-Cl bond lengths are 2.377(2),2.412(2) and 2.369(2)  for 1,and 2.376(2),2.414(1) and 2.383(2)  for 2,respectively.The electrochemical properties of these two complexes were studied in CH2Cl2 solution by cyclic voltammetry.     

Synthesis of a new salt containing polyoxometallate anion and M-Cu-S cluster cation [MS_4Cu_4(γ-MePy)_8][M_6O_19] (M = Mo,W).Crystal structure of [WS_4Cu_4(γ-MePy)_8][W_6O_19]

Reactions of (NH4)2MS4, AgBr and CuBr in r-methylpyridine produced one new compound, [MS4Cu4(r-MePy)8]M6O19] (1, M = W; 2, M = Mo), of which 1 was characterized by single crystal X-ray analysis. The crystal data: orthorhombic, Pbcn, a = 15.434(4),b= 16.732(2), c = 28.657(7) A, V = 7400.8(8) A3, Z = 4, R = 0.072 for 3121 independent data. The compound is the first example which contains both polyoxotnngstate anion and heteropolynuclear cluster cation. In the structure of the cation four edges of the tetrahedral WS42- core are coordinated by four copper atoms, giving a WS4Cu4 aggregate of approximate D2h symmetry. The differences between the reaction of Cu+ with MS42- and that of Ag+ with MS42- in pyridine and its derivatives are discussed.     

Synthesis, Characterization and Crystal Structure of [Co2Mo2(μ4-C2HPh)(μ-CO)4(CO)4(η5-C5H4C(O)Me)2]

The reaction of μ-alkyne-bridged dimolybdenum compound [Mo2(μ-C2HPh)(CO)4(η5-C5H4C(O)Me)2] 1 with Co2(CO)8 in refluxing toluene gave a new butterfly compound [Co2Mo2(μ4-C2HPh)(μ-CO)4(CO)4(η5-C5H4C(O)Me)2] 2 which was fully characterized by elemental analysis, IR, 1H NMR and X-ray single crystal diffraction techniques. 2 crystallized in monoclinic system, C30H20Co2Mo2O10, Mr=850.23, space group P21/a(#14), a=14.165(5), b=12.498(2), c=16.204(2)(A), β = 96.50(2)°, V = 2850(1)(A)3, Z = 4, Dc = 1.981 g cm-3, F(000)=1672, μ(MoKα)=20.41 cm-1, final R=0.030, Rw=0.039 for 4831 observable reflections with I>2σ(I). The structure contains a Co2Mo2 butterfly core, and each Mo-Co bond is spanned by an asymmetric semi-bridging carbonyl ligand.     

Synthesis, Structure and Optical Limiting （OL） Properties of a Novel Incomplete Cubane-like Cluster [PPh4][η^5-C5Me5） WS3-（CuBr） （CuI）2 （μ-dppm）]

IntroductionTetrathiometallateanions [MS4 ]2 - (M =Mo ,W )andtheirclusterswithvarioustransitionmetalsarewell knownfortheirrichcoordinationchemistry ,1 7andtheirrelationtoindustrialcatalysisprocess ,8biologicalsystems ,9andNLOmaterials .10 12 However,thechemistryoftheorganometallictrisulfidecomplexes [PPh4 ][(η5 C5Me5) MS3](M =Mo ,13W14 )andtheirrelatedmixed metalclus tershavebeenlessinvestigated .15,16 Inordertoextendourknowledgeaboutthechemistryof [PPh4 ][(η5 C5Me5) MS3]andconti…     

Synthesis and Crystal Structure of [(PPh3)(CH3COS)2NiB10H10]·0.4(C5H12)

The title compound [(PPh3)(CH3COS)2NiB10H10]·0.4(C5H12) has been synthesized by the reaction of [NiCl2(PPh3)2], closo-[B10H10]2- and CH3COSH in CH2Cl2 solution. It was recrystallized from n-pentane/CH2Cl2 solution and its structure was determined by X-ray diffraction analysis. The crystal is triclinic, space group P1, Mr=618.23, with a=10.049(1), b=12.638(2), c=14.077(2) , α=110.13(1), β=87.65(1), γ=96.01(1)°, V=1669.3(4)(A)3, Dc=1.230 g/cm3, Z=2, λ(MoKα)=0.71073(A), μ=7.76 cm-1, F(000)=642. The final refinement is converged with R=0.042 (5986 observed reflections with I≥2σ(I)), wR2 =0.151. The cluster is a nido eleven-vertex {NiB10} cage with the Ni atom in the open NiB4 face. Cyclizations resulting in two five-membered rings, Ni(7)-S(1)-C(1)-O(1)-B(2) and Ni(7)-S(2)-C(2)-O(2)-B(3), have occurred.     

Cleavage of the Fe—Fe Bond of （Me2SiSiMe2） [η^5－C5H4Fe（CO）2]2 with Na／Hg and Molecular Structure of the Ring－Opened Complex

The reaction of the rifle cyclic complex (1) with sodium amalgam in THF resulted in the expected cleavage of the Fe-Fe bond to afford his-sodium salt ( Me2SiSiMe2 ) [η^5-C5H4Fe(CO)2]2 (4). The latter was not isolated and was used directly to react with MeI, PhCH2Cl, CH3C(O)Cl, PhC(O)Cl,Cy3SnCl (Cy= cyclohexyl) or Ph3SnCl to afford corresponding ring-opened derivatives (Me2SiSiMe2) [η^5-C5H4Fe(CO)2]2 [5, R=Me; 6, R=PhCH2; 7, R=CH3C(O); 8, R=PhC(O); 9, R = Cy3Sn or 10, R = Ph3Sn ]. The crystal and molecular structures of 10 were determined by X-ray diffraction analysis. The molecule took the desired ant/ conformation around the Si-Si bond. The length of the Si--Si bond is 0.2343(3)nm, which is essentially identical to that in the cyclic structure of 1[0.2346(4) tun]. This result unambiguously demonstrates that the Si--Si bond in the cyclic structure of 1 is not subject to obvious strain.     

A novel heteropolymetalate containing Fe_4(OH)_4 segment: crystal structure of [Me_4N]_10[Fe_4(OH)_4(PW_10O_37)_2]·15H_2O

[Me4N]10[Fe4(OH)4(PW10O37)2] · 15H2O was synthesized by the reaction of FeCl3 ·6H2O, with △-Na8HPW9O34 and Me4NBr. Crystal data: M = 6225.75, space group P21/c with the monoclinic parameters: a = 1.3228(5), b = 3.5634(3), c = 1.5226(2) nm, β = 94.20(2)°, V = 7.1576nm3, 7 = 2,DC = 2.888 g/cm3, Mo Kαradiation (λ = 0.071069 nm), μ= 168.534 cm-1, F(000)=5576, final R = 0.0428 and Rw = 0.1204 for 7086 observed reflections with I > 2σ( I) . The structure of the title compound is the first structurally characterized heteropolymetalate with hydroxo-bridging metal aggregation Fe4OH4 encapsulated in the dimer of Keggin polyoxoanion.     

Cleavage of the Fe-Fe Bond of(Me_2SiSiMe_2)[η~5-C_5H_4Fe(CO)_2]_2 with Na/Hg and Molecular Structure of the Ring-Opened Complex

The reaction of the title cyclic complex(1) with sodium amal-gam in THF resulted in the expected cleavage of the Fe--Febond to afford bis-sodium salt (Me_2SiSiMe_2) [η~5-C_5H_4Fe(CO)_2Na]_2 (4). The latter was not isolated and was used di-rectly to react with MeI, PhCH_2Cl, CH_3C(O)Cl, PhC(O)Cl,Cy_3SnCl (Cy=cyclohexyl) or Ph_3SnCl to afford correspondingring-opened derivatives (Me_2SiSiMe_2) [η~5-C_5H_4Fe(CO)_2R]_2[5, R=Me; 6, R=PhCH_2; 7, R=CH_3C(O); 8, R=PhC     

Synthesis and Crystal Structure of [CpRu（η^5-C5H5）（dppc）Cl][PF6]

1INTRODUCTION The fragment[Ru(η5-C5H5)(PPh3)2Cl]plays an important role in the organo-ruthenium chemistry development,and has been used as a versatile star-ting material for other compounds due to its stability and facile manipulation.Much work has shown that a wide range of ligands with different steric and electronic properties can displace not only the Cl ligand but also the phosphine groups in[Ru(η5-C5H5)(PPh3)2Cl][1].The interest in this fragment and related derivatives concer…