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 .     

New Ruthenium Complexes of Fullerene C60＆C70

The new complexes[Ru(NO)(PPh3)]2(η^2-Cm)(m=60 1 or 70 2)have been prepared by heating a solution of C60(or C70)with[Ru(NO)2(PPh3)2]in toluene.They have been characterized by elemental analysis,IR,UV/VIS,XPS,^13C and ^13P NMR spectroscopy.The photovaltaic effect for the new compounds has been studied.     

Synthesis,Crystal Structure and Photophysical Properties of Cu（Ⅰ） Complexes Containing 2,5-Bis（pyridyl）-1,3,4-oxadiazole

Four novel Cu(Ⅰ) complexes,[Cu(o-PYO)(PPh3)2]BF4(1),[Cu(o-PYO)(DPEphos)]BF4(2),[Cu2 (o-PYO)(PPh3)3(CH3CN)](BF4)2(3) and [Cu2(o-PYO)(DPEphos)2 ](BF4)2(4) (o-PYO=2,5bis(pyridyl)-1,3,4-oxadiazole,PPh 3=triphenylphosphine,DPEphos=bis(2-(diphenylphosphanyl)phenyl)ether),have been synthesized and characterized by 1 H NMR,elemental analysis and single-crystal X-ray diffraction.The central cuprous ions in all complexes are surrounded by N and P atoms to form a distorted tetrahedral geometry,although one of the cuprous ions in complex 3 is coordinated by a PPh3 and an acetonitrile molecule due to the steric hindrance and weak coordination ability from monodentate PPh3 ligand.The UV-vis absorption spectra in CH2Cl2 show the characteristic metal-to-ligand charge transfer (MLCT) absorption bands in the region of 360-480nm.Four Cu(I) complexes exhibit yellow to orange-red phosphorescence with the emission maximum at 572,577,562 and 597nm,respectively in the solid state.     

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.     

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.     

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.     

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.     

CRYSTAL STRUCTURE OF（η^5—C5H5）GdCl2（THF）3

<正> Compound (η5-C5H5)GdCl2(THF)3 was successfully prepared from action of GdCl3 and NaC5H5 in tetrahydrofuran (THF). X-ray diffraction data were collected at low temperature (about 210K). Its crystal belongs to the monoclinic space group P 21/n with a = 7. 821(2), b = 17.068(1), c=15. 057(1)(?), β=94. 76 (2)°, V = 2003. 2(10)(?)3, Z = 4, Dc=1. 69g/cm3, F(000)=1012, Mr=509. 6. The structure was solved by heavy-atom method. Least-squares refinement converged to a final R value of 0. 050. The coordination number of the Gd atom is 8. The centre of the cyclopentadienyl, the two Cl atoms and the three oxygen atoms of THF molecules form a distorted octahedron about the Gd atom.     

Synthesis and Structure of a Ruthenium（Ⅱ）-dithiocarbamate Complex [RuH（CO）（PPh_3）_2（4-ClPhNHCS_2）]·C_6H_（14）

The title complex [RuH(CO)(PPh3)2(4-ClPhNHCS2)]·C6H14 has been prepared and characterized by X-ray diffraction analysis.It crystallizes in the triclinic system,space group P1 with a = 11.0817(2),b = 14.3889(2),c = 15.2136(2) ,α = 71.018(1),β = 74.911(1),γ = 85.146(1)°,V = 2214.86(6) 3,Z = 2,Mr = 900.4,Dc = 1.350 g/cm3,Mr = 900.40,μ(MoKα) = 0.616 mm-1,F(000) = 926,S = 1.016,the final R = 0.0478 and wR = 0.0947 for 6828 observed reflections with I > 2σ(I) and 505 variables.The molecular structure of 1 consists of one neutral complex [RuH(CO)(PPh3)2(4-ClPhNHCS2)] and one hexane solvent molecule.The geometry around ruthenium is pseudo-octahedral with two trans-binding PPh3 ligands and one chelating bidentate 4-ClPhNHCS2- ligand via two sulfur atoms.The average Ru-S,Ru-P and Ru-H bond lengths are 2.4824(8),2.3495(8) and 1.71(2),respectively.The electrochemical properties of 1 have been studied in CH2Cl2 solution by cyclic voltammetry.     

Synthesis and Structure of an Iridium(Ⅲ)-ferrocenyl-dithiophosphonate Complex [{Fc(OCH_3)PS_2}Ir(cod)] (Fc=Fe(η~5-C_5H_4)(η~5-C_5H_5),cod=1,5 Cyclooctadiene)

The title complex [Fc(OCH3)PS2Ir(cod)] (1, Fc = Fe(η5-C5H4)(η5-C5H5), cod = 1,5-cyclooctadiene) has been prepared and characterized by X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/n with a = 12.5567(5), b = 13.5197(5), c = 11.7833(4) , β = 99.651(2)°, V = 1972.06(13) 3, Z = 4, Mr = 611.52, Dc = 2.06 g/cm3, μ(MoKα) = 7.775 mm·1, F(000) = 1184, S = 1.063, the final R = 0.0199 and wR = 0.0468 for 4063 observed reflections with I > 2σ(I) and 227 variables. The molecular structure of 1 shows that the central iridium atom is chelated by the [Fc(OCH3)PS2]-ligand via two sulfur atoms and coordinated by one η4-cod molecule via four carbon atoms in a distorted octahedral coordination geometry. The average Ir-S and Ir-C bond lengths are 2.3712(8) and 2.122(3) , 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 Crystal Structure of a Ruthenium(II) Compound of Dinitrogen

The title compound [Ru(bph)(PPh3)2(N2)]·(PF6)·1.5CH2Cl2 (bph = N-(benzoyl)- N?-(picolinylidene)-hydrazine) has been prepared and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group P21/n with a = 13.5201(6), b = 15.5078(6), c = 25.0656(13) ?, β = 100.257(3)°, C50.50H43Cl3F6N5OP3Ru, Mr = 1150.23, V = 5171.4(4) ?3, Z = 4, F(000) = 2332, Dc = 1.477 g/cm3 and μ(MoKα) = 0.615 mm-1. The structure was refined to R = 0.0524 and wR = 0.1398 for 8060 observed reflections (I > 2σ(I)). The Ru-N2 and N(N bond distances are 1.919(4) and 1.133(5) ?, respectively.     

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 Crystal Structure of the Diiron Azadithiolate Complex [（μ-SCH_2）_2NPh]Fe_2（CO）5（Ph_2PCH_2PPh_2）

Reaction of [(μ-SCH2)2NPh]Fe2(CO)6 with Ph2PCH2PPh2 in the presence of Me3NO·2H2O gave the title complex [(μ-SCH2)2NPh]Fe2(CO)5(Ph2PCH2PPh2)(1)in 78% yield.The new complex 1 was characterized by elemental analysis,spectroscopy and X-ray crys-tallography.It crystallizes in triclinic,space group P1 with a = 10.832(2),b = 12.003(2),c = 15.579(3),V = 1785.6(6)3,Z = 2,C32H26Fe2NO5PS2,Mr = 819.40,Dc = 1.524 g/cm3,μ(MoKα)= 1.064 mm-1,F(000)= 840,T = 113(2)K,the final R = 0.0543 and wR = 0.1218 for 6203 observed reflections(I > 2σ(I)).The Ph2PCH2PPh2 ligand resides in an axial position of the square-pyramidal coordination sphere of the Fe atom and trans to the benzene ring in order to reduce the steric repulsion between Ph2PCH2PPh2 and the benzene ring.     

Ru-catalyzed highly enantioselective hydrogenation of α-keto Weinreb amides

Asymmetric hydrogenation of α-keto Weinreb amides has been realized with [Ru((S)-Sunphos)(benzene)Cl]Cl as the catalyst and CeCl 3·7H2O as the additive.A series of enantiopure α-hydroxy Weinreb amides(up to 97% ee) have been obtained.Catalytic amount of CeCl3·7H2O is essential for the high reactivity and enantioselectivity and the ratio of CeCl3·7H2O to [Ru((S)-Sunphos)(benzene)Cl]Cl plays an important role in the hydrogenation reaction.     

取代四甲基环戊二烯基钌羰基化合物的合成及晶体结构(英文)

The ligands (C5Me4R) [R =n-Butyl (1), Benzyl (2), PhMe-2 (3)] reacted with Ru3(CO)12 in refluxing xylene to give corresponding new substituted tetramethylcyclopentadienyl diruthenium metal carbonyl complexes [(η5-C5Me4R)Ru(CO)( μ-CO)]2 [R=n-Butyl (4), Benzyl (5), PhMe-2 (6)], respectively. The three new complexes were characterized by elemental analysis, IR and 1H NMR spectra. The crystal structure of complex 5 was determined by single crystal X-ray diffraction. The X-ray crystal structure of complex 5 confirms the structure with bridging and terminal CO groups. CCDC: 709601.     

NITROSYL COMPLEXES——SYNTHESIS, CHARACTERIZATION AND CRYSTAL STRUCTURES OF (η~5-C_5_H_5)M(CO)_2NO AND (η~5-C_5H_5)M(μ_3-NH)(μ_2-NO)(μ_2-CO)Fe_2(CO)_6(M=Mo OR W)

Treatment of tricarbonyl cyclopentadienyl metal (molybdenum or tungsten) chloride with equal molar amounts of tricarbonyl nitrosyl iron sodium at room temperature yielded the following complexes: orange (η5-C5H5)M(CO)2NO, violet [(η5-C5H5)M(CO)3]2 and black (η5-C5H5)M(μ3-NH)(μ2-NO)(μ2-CO)Fe2(CO)6. These were separated and purified by column chromatography. The last black complexes have a new cluster-type structure with a face-bridging imido(μ3-NH) ligand which was obtained by reducing the nitrosyl (NO) group. In this paper, synthesis and characterization of the title complexes are reported along with their crystal structures which are of two types.     

Construction of a Set of Cadmium（Ⅱ） Coordination Polymers with Atza and 2,2′-Bipy or 1,10-Phen Ligands （Atza=5-Aminotetrazole-1-acetato Anion）

Reactions of CdX2(X=NO3-, ClO4-) with Hatza (atza=5-aminotetrazole-1-acetato anion) and 2,2′-bipyridine (2,2′-bipy) or 1,10-phenanthroline (1,10-phen) in a methanol/aqueous solution produced a set of new Cd(Ⅱ) coordination polymers, {[Cd(atza)(H2O)(2,2′-bipy)]ClO4}n (1), {[Cd(atza)(H2O)(1,10-phen)]ClO4 }n (2), {[Cd(atza)(H2O)(2,2′-bipy)]NO3}n (3) and {[Cd(atza)2 (1,10-phen)]·0.5H2O}n (4). Single-crystal X-ray diffraction analysis reveals that each Cd(Ⅱ) ion has a distorted octahedral coordination geometry in 1-4, and the Cd(Ⅱ) ion centers are connected through the tridentate atza bridging ligands to form a 2D layer (1-3) or ID chain (4) structure. The fluorescent properties of 2 and 4 are also 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 Ring-opening Metathesis Polymerization of η~5-Pentamethylcyclopentadienyl-(η~5-exo-tricyclo [5.2.1.0~(2,6)]deca-2,5,8-trien-6-yl) Iron

η5-Pentamethylcyclopentadienyl-(η5-exo-tricyclo[5.2.1.02,6]deca-2,5,8-trien-6-yl) iron(3) was synthesized and characterized by 1H NMR, 13C NMR, MS, elemental analysis, IR, UV and X-ray diffraction analysis. Compound 3 was polymerized with ring-opening metathesis polymerization(ROMP) initiator (PCy3)2Cl2Ru=CHPh. 1H NMR and IR spectra revealed the presence of CH=CH units in the polymer and supported the ROMP mechanism. GPC analysis of the polymer showed that the weight-average molecular weights(Mw) was 5967, ...