SYNTHESIS,CHARACTERIZATION AND CRYSTAL STRUCTURES OF η~5-CH_3C_5H_4)M(CO)_2NO AND(η~5-CH_3C_5H_4)M(μ_3-NH)(μ_2-NO)(μ_2-CO)Fe_2(CO)_6(M=Mo or W)

Synthesis of complexes(η~5-CH_3C_5H_4)M(CO)_2NO(M=Mo,I;M=W,II)and clusters(η~5-CH_3C_5H_4)M(μ~3-NH)(μ~2-NO) (μ~2-CO)Fe_2(CO)_6(M=Mo,III:M=W,IV),based on the reaction of (η~5-C5_H_4)M(CO)_3Cl with Na[Fe(CO)_3NO] at room tem-perature,have been demonstrated,The crystal structures of II and IV arealso presented.     

亚硝酰基配合物——Ⅱ.(η~5-C_5H_5)M(CO)_2NO和(η~5-C_5H_5)M(μ_3-NH)(μ_2-NO)(μ_2-CO)Fe_2(CO)_6(M=Mo或W)的合成、表征和晶体结构

在四氢呋喃-甲醇介质中将环戊二烯基三羰基金属(钼或钨)氯化物与等摩尔羰基亚硝酰基钠盐在室温反应,产物经柱色谱分离和纯化得:橙色固体(η~5-C_5H_5)M(CO)_2NO、紫色固体[(η~5-C_5H_5)M(CO)_3]_2和黑色固体(η~5-C_5H_5)M(μ_3-NH)(μ_2-NO)(μ_2-CO)Fe_2(CO)_6(M=Mo或W)各两种.其中,后者是具有新颖结构的簇合物,分子中含有亚硝酰基(NO)被还原得到的亚胺基(μ_3-NH)配体.本文报道了它们的合成、表征和两种配合物X射线晶体结构研究的结果.     

MOLYBDENUM-IRON MIXED METAL CLUSTERS (Ⅰ)——THE SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF (η~5-C_5H_5)_2Mo_2Fe_2(μ_4-Te)(μ_3-Te)_2(CO)_6

The reaction of Fe_2(μ_3-Te)_2(CO)_9 with Mo_2(CO)_6(η~5-C_5H_5) affords the title compound. Its X-ray analysis shows a butterfly structure for the Mo_2Fe_2 core; the two molybdenum atoms occupy the hinge with a Mo—Mo bond distance of 2.819 and the two iron atoms are on the tops of the wings with an average Mo—Fe bond distance of 2.932(2). Each molybdenum is bonded to a Cp ring, and three CO ligands are terminally bonded to each iron atom. One tellurium atom quadruply bridges Mo_Fe_2 with Mo—Te(μ_4)=2.625(2). and Fe—Te(μ_4)=2.713(2). Two tellurium atoms triply bridge the two triangular Mo_2Fe faces with Mo—Te(μ_3)=2.678(1) and Fe—Te(μ_3)=2.513(3). The molecule has C_(2v) symmetry and a bicapped triangle bipyramidal skeleton. Crystallographic parameters are as follows: space groupImm2(orthorhombic), a=14.562(3), b=10.391(1), c=7.139(4), V=1080.2(i)~3, Z=2, ρ(cald)=1.819g·cm~(-3). The final R factor was 2.2％ for 620 independent reflections(I>2σ(I)).     

CRYSTAL STRUCTURE OF MIXED-METAL CLUSTER(η~5-C_5H_5)_2Mo_2Fe_2(μ3-S)_2(μ-CO)_2(CO)_6

<正> Mr= 721.98,monoclinic, P21/n,a= 9.773(1), b = 6.641(3), c = 16.258(1)A,β=92.25(1)°,V=1054.4(7)A3,Dx = 2.274g/cm3,Z=2,λ(MoKα)=0.7107A.Final R= 0.024,Rw= 0.036 for 1554 observed reflections. The cluster core Fe2Mo2 is a rhombic plane with Mo-No distance of 2.827A and average Mo-Fe distance of 2.773A.     

CRYSTAL STRUCTURE OF THE MIXED-METAL CLUSTER,(η~5-C_5H_5)_2Mo_2Fe_2(μ_4-Se)(μ_3-Se)_2(CO)_6

<正> Mr=838.71, monoclinic, P21/m, a=8.245(4), b=15.504(5), c=8.242(4) A,β=101.50(4)°,V=1032.5(1.5)A3, Dx=2.698 g/cm3, Z=2,λ(MoKα)=0.7107A. Final R=0.040, Rw=0.045, for 1460 observed reflections.     

CRYSTAL STRUCTURE OF FeaTe_2(CO)_6(NO)(η_5-C_5H_5)

<正> The title compound belongs to triclinic system, space group PI, with dimensions: a = 9.237(1), b = 9.589(1), c = 10.424(1) A ; <*= 72.09(2)?ft- 88.79(2)? 3r=80.28(l)? Z = 2, V = 865.5 A3, Dx = 2.626 gcnr3. Final R = 0.026 and Rw = 0.036 for 2531 reflections.     

钼铁混合金属原子簇的研究Ⅱ(η~5-C_5H_5)_2M_(o2)F_(e2)(μ_3-T_e)_2(μ_3-CO)-(μ_2-CO)(CO)_5的合成及结构

钼铁混合金属原子簇Mo_2Fe_2Te_2(CO)_7(η~5-C_5H_5)_2是Fe_3Te_2(CO)_9与Mo_2(CO)_6(η~5～C_5H_5)_2反应所得的产物之一。它的晶体属正交晶系,空间群为Pbn2_1。晶胞参数:a=12.172(5);b=13.595(2);c=12.924(4)A,V=2138.5(2)A~3。晶体结构由直接法及差值Fourier合成解出,经最小二乘法修正,最终R因子为0.030(3233个Ⅰ>26(Ⅰ)的反射)。在簇分子中,四个金属原子呈四面体构型,两个μ_8-Te原子和一个不对称的μ_8-CO分别桥连到四面体的三个三角面的金属原子上,从而构成了缺顶点的类立方烷结构。     

CRYSTAL STRUCTURE OF MIXED-METAL CLUSTER (η~5-C_5H_5)_2W_2Fe_2(μ_3-S)_2(CO)_8

<正> (η5-C5H5)W2Fe2(μ3-S)2(CO)8,Mr = 897. 80,monoclinic,C2/c,a= 18. 019 (2),b = 8. 330(1),c= 16. 043(2) A ,β= 114. 30(1)°,v = 2194. 7(6)A3,z= 4, Dx = 2. 717g/cm3, A(MoKa) = 0. 71037 A , μ= 122. 01cm-1, F (000) = 1656, T = 295K,R=0.056,Rw = 0. 059 for 1250 observed reflections. The crystals of the title compound are isomorphous with the analog (η5-C5H5)2Mo2Fe2(μ3-S)2(CO)8.     

SYNTHESIS AND CHARACTERIZATION OF (PPh_3)_3Co(μ-CO)_2 V(CO)_2Cp AND (PPh_3)

ＳＹＮＴＨＥＳＩＳＡＮＤＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮＯＦ（ＰＰｈ_３）_３Ｃｏ（μ－ＣＯ）_２Ｖ（ＣＯ）_２ＣｐＡＮＤ（ＰＰｈ_３）ＨＰｔ（μ－ＣＯ）（μ－ＰＰｈ_２）Ｖ（ＣＯ）_２ＣｐＣｈａｎｇＰｉｎｇＳＨＡＯ（ＤａｌｉａｎＩｎｓｔｉｔｕｔｅｏｆＣｈ?..     

SYNTHESIS AND CRYSTAL STRUCTURE OF [(η~5-C_5H_5)_2NdCl·OC_4H_8]_2

All attempts to prepare light lanthanide dicyclopeutadienyt chloride failed,due to the disproportionation reaction. The crystal complex of [(η~5-C_5H_5)_2NdCl.OC_4H_8]_2 was successfully prepared by the reaction of NdCl_3·2C_4H_8O with cyclopentadienyl sodium (molar ratio 1:1.8)in tetrahydrofuran at room temperatureThe composition of the title compound was determined by the methods of elemental analysis, infrared spectroscopy and photoelectron spectroscopy. The crystal structure of [(η~5-C_5H_5)_2NdCl·OC_4H_8]_2 was determined from single crystal X-ray diffraction. Data were collected at-60℃ under dry nitrogen atmosphere.The complex crystallizes in the monoclinic space group P2_1/c,with Z=2. Lattice parameters are: a=8.201(3), b=21.589(6),c=8.596(3),β=109.10(3)°.The structure was solved by Patterson and Fourier techniques and refined by least-squares to a final conventional R=0.0636 for 1680 reflections. There are two Nd atoms in the dimeric unit which are bridged asymmetrically by the two chlori     

SYNTHESIS AND CRYSTAL STRUCTURE OF PdCl_2(dppf)·0. 5(CH_3)_2-CO(dppf=(η~5-C_5H_4PPh_2)_2Fe)

<正> C35.5H31FePdCl2O0.5P2 ({dichloro-[1,1' -bis (diphenyl) phosphino]-fer-rocene}palladium (Ⅱ) hemi acetone solvate) ,Mr = 760. 74,monoclinic,space group C2/ c,a=33. 993(4),b=10. 424(3),c=18. 364(4) A ,β=104. 52(1)°,V = 6299A3,Z= 8,DC=1.67 g/cm3,μ= 13. 3cm-1,F(000) = 3200,final R= 0.075 for 2058 observed reflections. The environment of the Pd atom is described as a square plane with two cis-chlorine atoms and two phosphorus atoms. The [1, 1'-bisdiphenylphospino] ferrocene (dppf) group is connected to the Pd atom as a bidentate ligand. The Pd-P distances are 2. 278(5) and 2. 278(6) A ;the Pd-Cl distances 2. 323(6) and 2. 345(6) A.     

SYNTHESIS AND CRYSTAL STRUCTURE OF {C(η~5-C_5H_5)_4Nd_4(μ_4-O) (μ_2-Cl)_8)]·[Li(dme)_2THF]_2

<正> The reaction of (η5-C5H5)3Nd·THF and NdCl3·2LiCl·nTHF in solution at room temperature gave rise to[(η5-C5H5)4Nd4(μ4-O)(μ2-Cl)8][Li(dme)2THF]2 (Mr = 1654.44). Crystals of the compound were obtained at about - 10℃. The intensity data were collected under nitrogen atmosphere at-60℃. The crystal belongs to the rhombic system with space group Pna21 and the unit cell parameters : a=19. 010(7),b = 23. 231(6) ,c= 14. 180(4) A ;V = 6261. 91 (A3) , DC= 1. 67 (g/cm3), λ(MoKa) = 0. 71069A,F(000) = 3240,μ(mm-1) = 3. 660;Z = 4. Least-squares refinement with anisotropic temperature factors for all non-hydrogen atoms led to the final R=0. 054, Rw = 0. 056. The molecule is made up of the anion group and the cation. The oxygen atom links four Nd3+together as μ4-bridge. The eight chlorine atoms form the eight chlorine-bridge bonds among four Nd3+ions. The average bond length is : Nd-O=2. 374,Nd-Cl = 2. 811,Nd-C=2. 777,Nd(a)- Nd(b) = 3. 872A.The bond angles of Nd(a) -Nd (b)-Nd(c) fall in the range of 62~63°,th     

Nitrosyl Complexes 6.Reactions of Na[Fe(CO)_3NO]with Cp~*M(CO)_3Cl(Cp~*=η~5-CH_3C_5H_4,M=Mo or W):Crystal structures of Cp~*M(CO)_2NO and Cp~*M(μ_3-NH)(μ_2-NO)(μ_2-CO)Fe_2(CO)_6

Sodium nitrosylcarbonyliron reacts with methylcyclopentadienylcarbonylmetal(Mo orW)chloride in CH_3OH/THF at room temperature to give CpMo(CO)_2NO(1a)(Cp=η~5-CH_3C_5H_4)or CpW(CO)_2NO(1b),[CpMo(CO)_3]_2(2a)or[CpW(CO)_3]_2(2b),and CpMo(μ3-NH)(μ2-NO)-(μ2-CO)Fe_2(CO)_6(3a)or CpW(μ3-NH)(μ2-NO)(μ2-CO)Fe_2(CO)_6(3b),respectively.Complexes1a,1b,3a and 3b were analyzed by IR,NMR,MS and elemental analyses,and the crystalstructures of 1b,3a and 3b were determined by X-ray diffraction method.The new clusters 3aand 3b have μ3-NH ligands which were formed by redaction of NO in the synthetic reactions.     

A NOVEL REACTION BETWEEN [μ-PhC(O)S]-(μ-RS)Fe_2(CO)_6 AND (μ-R~1S)(μ-XMgS)Fe_2(CO)_6——THE SYNTHESIS, CHARACTERIZATION AND FORMATION MECHANISM OF TWIN CLUSTER COMPLEXES [(μ-RS)Fe_2(CO)_6](μ_4-S)[(μ-R~1S)Fe_2(CO)_6]

The reaction of (μ-RS)(μ-XMgS)Fe_2(CO)_6 with PhC(O)Cl gave four new benzoyl complexes [μ-PhC(O)S](μ-RS)Fe_2(CO)_6(R=Me, Et, n-Bu, CH_2=CHCH_2), which further reacted with (μ-R~1S)(μ-XMgS)Fe_2(CO)_6 to afford eight new twin cluster complexes with the general formula of [(μ-RS)Fe_2(CO)_6](μ_4-S)[(μ-R~1S)Fe_2(CO)_6]. The single crystal X-ray analysis for one of these complexes (R=n-Bu, R~1=Ph) showed that it consists of two different moieties PhSFe_2(CO)_6 and n-BuSFe_2(CO)_6 joined together through the spiran type of μ_4-S., The complex belongs to space group P-1; cell parameters are a=9.028(3), b=10.386(1), c=16.723 (5); α=87.70(2)°,β=75.67(2)°, r=82.26(2)°; z=2, Dx=1.743 g/cm~3. Final deviation factor R=0.031.     

SYNTHESIS of(η~5-C_9H_7)Ln(η~8-C_8H_8)·2THF AND CRYSTAL STRUCTURE OF(η~5-C_9H_7)Pr(η~8-C_8H_8)·2THF

The reaction of LnCl_3 with K _9H_7(C_9H_7=indenyl)andK_2C_8H_8(C_8H_8=cyclooctatetraene)in tetrahydrofuran(THF)give thecorresponding complexes(η~5-C_9H_7)Ln(η~8-C_8H_8)·2THF.The synthesis of(η~5-C_9H_7)Ln(η~8-C_8H_8)·2THF(Ln=Pr,Nd)and crystal structure of(η~5-C_9H_7)Pr(η~8-C_8H_8)·2THF are described.     

Synthesis and Characterization of the Chiral Skeleton Cluster [NiRuMo(CO)_5(μ_3-S)(η~5-C_5H_5)(η~5-C_5H_4COCH_3)]

1 INTRODUCTION The chemistry of transition metal cluster has enjoyed an exceptional growth since the mid 1970s[1, 2], especially in recent years the structural and bonding aspects of mixed-metal tetrahedral skeleton clusters have been extensively studied[3]. One important reason is that such chiral cluster can induce an asymmetric catalysis potentially. In our research group, considerable efforts have been directed to the synthesis of chiral tetrahedral clusters containing four different…     

Synthesis and characterization of tris(η~5-cyclopentadienyl-μ-carbonyliron)-μ_3-nitrosyl cluster:X-ray structure of[(η~5-C_5H_5)(μ-CO)Fe]_3(μ3-NO).C_4H_8O

Tris)(η 5-cyclopentadienyl-μ-carbonyl-iron)-μ3-nitrosyl cluster was obtained from the reaction of cyclopentadienyl dicarbonyliron dimer with nitrogen monoxide in xylene. The cluster was characterized by elemental analyses, IR, MS and 1H NMR. The crystal structure of [(η5-C5H5)(μ-CO)Fe]3(μ3-NO).C4H8O was determined by X-ray diffraction analysis. It crystallizes in the orthorhombic space group Pnma, a=9.053(2), 6=10.545(2), c=22.525(4) A, V=2150.3(7) A3, Z=4,Dc=1.68 g.cm-3; structure solution and refinement based on 1141 reflections with I > 3.0 (I) (MoKa, A=0.71073 A) converged at R=0.0540. The infrared absorption band at 1325 cm-1 of the μ3-NO in the cluster, which is red shifted, shows that μ3-NO is activated.     

SYNTHESIS AND STRUTURE OF THE FIRST INTERSTITIAL μ_7-S CLUSTER Co_7(μ_7-S)(μ_4-PSEt)(μ-SEt)_2(μ-CO)_2(CO)_(12)

The reaction of Co_2(CO)_8 with EtSPCl_2 gives a new crystal like compound Co_7(μ_7-S)(μ_4-PSEt)(μ-SEt)_2(μ-CO)_2(CO)_(12),whose structure has been determined by single crystal x-ray diffraction.This special com-pound reveals some new features in cluster chemistry~1:The fragmentation of a ligand precursor EtSPCl_2 yieldsthree kinds of fragments,μ_7-S,μ_4-PSEt and μ-SEt,which are ligands in the same cluster molecule.There is anew type of bridging S presented——A μ_7-S atom is interspaced into seven Co core.     

面桥亚硝酰基环戊二烯基羰基铁簇合物[(η~5-C_5H_5)(μ_2-CO)Fe]_3(μ_3-NO)的合成和表征

亚硝酰基配合物中存在着线型端基(三电子基)、弯曲型端基(单电子基)、桥式和面桥式不同的亚硝酰基配位方式,这些不同配位方式在催化研究领域中的应用具有无限广阔的前景。特殊的配位方式使中心原子出现16 e结构或20 e结构,在其它配合物中只有当配体解离或缔合时才拥有这样的电子结构,因而大部分亚硝酰基配合物均具有催化活性。其次配位亚硝酰基受中心原子活化使N≡O键容易断裂,亚硝酰基被还原生成羟胺或亚胺基;活化的亚硝酰基可以作为氧源催化转化汽车废气:2NO+2CO→N_2+2CO_2或2NO+CO→N_2O+CO_2以消除污染。我们曾在室温、常压下合成亚硝酰基配合物并     

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…