Synthesis and Crystal Structure of Binuclear Oxomolybdenum(VI) Complex with Both o-Mercaptophenolate

The complex (Bu4N) 2 [Mo2O5 (mp)2] was synthesized by the reactionof (Bu4N)2[Mo8O26] with H2mp (H2mp=o-mercaptophenol) in methanol. The molecular formula is C44H80Mo2N2O7S2, M.=1005.10. The complex is crystallized in monoclinic, space group P21/n with unit cell parameters, a = 17. 829 (2) A, b= 13. 759 (2 )A,c= 21. 974(2) A, g=105. 386(8)°, V= 5197. 4(1) , Dc= 1. 285 g/cm3, Z=4,λ(MoKa) =0. 71073 , μ=0. 607 mm-1,F(000) = 2120, final R=0.0348 and wR=0. 0741 for 4912 independent observed reflections (FM>4σ(Fo) ). Two MoO5S units inthe complex molecule exhibits the con facial distorted bioctahedral geometry and possesses an approximate C2 symmetry.

Solid-state Synthesis at Low-heating Temperature and Crystal Structure of a Dinuclear Molybdenum Complex with Oxalate Ligand[Bu_4N]_2[Mo_2O_2(OH)_2Cl_4(C_2O_4)]

The title compound was synthesized by the solid-state reaction of (NH_4)_6Mo_7O_(24)·4H_2O, Na_2C_2O_4, NH_2OH·HCl and Bu_4NBr at 90 ℃ for 10 h and crystallized from acetone-ether. The green crystal belongs to the monoclinic space group P2_1/n with a=9. 908(2), b= 17, 873(2), c= 13/450(2) A , β= 90. 09(1 )°,V = 2381. 6 (7 ) A￣3 , D_c = 1. 359 g/cm￣3 , Z= 2. The structure was refined to R =0. 0427 for 2562 reflections. The anion of the title compound can be described as an oxalate ligand (C_2O4￣2 ) bridging two [MoCl_2O(OH)] units, which contain Mo(V)atoms.

Syntheses, Crystal Structures and NMR of Two Molybdenum Complexes with 2,3-Dihydroxynaphthalene

Two complexes [H3N（CH2）2NH2]2[MoO2（C10H8O2）2] （1） and （C7H10N2）2- [MoO2（C10H8O2）2] （2） were obtained at nearly the same reaction condition and characterized by IR, 1H and 13C NMR and single-crystal X-ray diffraction. Both of the complexes possess complex anion [MoO2（C10H8O2）2]2- which shows a pseudo-octahedrally coordinated fashion. In complex 1, ethyldiamine presents just as a cation. However, in complex 2, ethyldiamine combines with the acetyl acetone as a byproduct which is confirmed by NMR.

THE FIRST BINUCLEAR MOLYBDENUM AND TUNGSTEN COMPLEXES WITH DOUBLY-BRIDGING PYRIDINE-2-THIOLATO LIGANDS.X-RAY CRYSTAL STRUCTURE OF THE COMPLEX[Mo_2(CO)_4(μ-pyS)_2(PPh_3)_2].2C_7H_8

The title complex was obtained by reactions of [Mo(CO)_3(MeCN)_3] with [CuBr(pySH)(PPh_3)_2]or directly with pySH and PPh_3. The latter method can be used to synthesize the corresponding tungsten complex [W_2(CO)_4(μ-pyS)_2(PPh_3)_2].The molecular structure of the title compound was determined by X-ray diffraction method.

Synthesis and Crystal Structure of cis-Bis(3-hydroxy2-ethyl-4-pyranonato)dioxomolybdenum(Ⅵ)

The complex MoO2(C7H7O3)2 has been prepared by the reaction of 3-hydroxy- 2-ethyl-4-pyranone with (NH4)6Mo7O244H2O. The single-crystal X-ray study shows that the coordination sphere about the molybdenum atom in the complex consists of six oxygen atoms arranged in a distorted octahedral geometry with the dioxo ligands in cis positions. The crystal is of monoclinic, space group P21/c with a = 8.3968(2), b = 12.7534(4), c = 14.5443(4) ? b = 96.277(1), V = 1548.18(7) ?, Z = 4, C14H14O8Mo, Mr = 406.19, Dc = 1.743g/cm3, m = 0.886mm-1, F(000) = 816, R = 0.0444 and wR = 0.1091 for 2336 observed reflections with I>2s(I). The average Mo=O bond length is 1.695(4) ? The two ketonic oxygen atoms of the pyranone moieties are trans to the oxo ligands and the hydroxy oxygen atoms are trans to each other. The average MoO bond lengths are 2.248(4) ?for the ketone oxygens and 2.005(3) ?for the hydroxy oxygens. The average ligand bite angle of OMoO is 75.2(2) and the bond angle between two Mo=O is 105.1(2). The dihedral angle is 79.16(2)?between two chelate ring planes.

Synthesis and Crystal Structure of a Molybdenum Carbonyl Compound with Thiolate and Dithiocarbamate Ligands, [Bu_4N][(OC)_4Mo(μ-SC_6H_5)_2Mo(C_5H_(10)CNS_2)(CO)_2]

A di-molybdenum carbonyl compound containing thiolate and dithiocarbamate ligands, [Bu4N][（CO）4Mo（μ-SC6H5）2Mo（C5H10dtc）（CO）2] 1 （CsH10dtc = S2CNC5H10）, has been prepared by reaction of [Mo2（SC6H5）2（CO）8] with C5H10dtcNa and [NBu4]Br in acetone. It crystallizes in monoclinic, space group P21/n with a = 13.162（3）, b = 17.466（2）, c = 20.453（4） A,β= 100.77（1）°, Z = 4, V= 4619（2）A^3, C40H56Mo2N2O6S4, Mr = 980.95, De= 1.389 g/cm^3,μ = 7.66 cm^-1, F（000） = 1988 and R = 0.0746 for 5161 observed reflections with I 〉 2σ（I）. The complex contains a [Mo2S2]^2- planar core in which one Mo atom is chelated by a C5H10dtc ligand, leading to different coordination environments of the two Mo atoms. 95Mo NMR measurement indicates that the two Mo atoms are in different oxidation states.

Crystal Structure and Spectrum Character of Bis[1-(4-Methoxyphenyl)-3-(1H-1,2,4-Triazol-1-yl)-1-Propanone] dichorozinc(Ⅱ) Complex

The titled new complex was synthesized and determined by X-ray diffraction. The crystal belongs to monoclinic, P-I group, a=1.8997（4）nm, b-0.581 07（12）nm, c=2.4209（5）nm, β-90.65（3）°, V=2.672 2（9） nm^3, Z=4, Dc= 1.488 g/cm^3, It has C2 symmetry with the axis through the Zn atom, and the zinc atom is coordinated by two N atoms of the 1-（4-methoxyphenyl） 3-（ 1H-1, 2, 4-triazol-1-yl）-1-propanone ligands and two C1^- atoms, forming a slightly distorted tetrahedron. Intermolecular hydrogen bonds make the complex stable. IR and electronic spectra study of the target complex were also carried.

Synthesis and Crystal Structure of(Et_4N)_3[{V(o-C_6H_4OS)_3}_2Na]

Et_4N)_3 [V(mp)_3Na(mp)_3V] was obtained from the reaction of (NH_4)_3VS_4, FeCl_2, Na_2mp(H_2mp=o-mercaptophenol,o-HSC_6H_4OH) and Et_4NCl in CH_3CN. C_(60)H_(84)N_3NaO_6S_6V_2, M_r=1260. 61, monoclinic, space group C2/c with a=24. 825(8) . b=14.716(5) , c=18. 419(10)A,β=94. 57(3)°, V=6707. 54 A￣3;Z=4, Dc=1. 248 g/cm￣3. μ= 5. 002 cm￣(-1). F(000)=2664. The structure was solved by direct methods and refined to final R(Rω)=0.059(0.059) for 3183 observed reflections with I≥2.5σ(I). The centrosymmetric anion of the title compound contains two [V(mp)_3]￣(2-) fragments linked by a sodium ion, the crystallographic center of symmetry , through the μ2-O bridges. The Ⅴ(Ⅳ) atom is in a coordination environment intermediate between a trigonal prism and an ideal octahedron.

Synthesis and Crystal Structure of Mo(CO)_4(NNP) (NNP=2-(N-Cyclohexyl-N-diphenylphosphinomethyl)aminopyridine)

The crystal structure of the title complex, Mo(CO)4(NNP), (NNP=2-(N-cyclohexyl- N-diphenylphosphinomethyl)aminopyridine) has been determined, and its crystallographic data are as follows: triclinic, space group P , a = 9.135(1), b = 9.772(1), c = 17.000(2) , a = 76.377(2), b = 78.333(2), g = 67.243(2)? Mr = 582.44, V = 1349.7(3) 3, Z = 2, Dc = 1.433 g/cm3, m(MoKa) = 0.581 mm-1 and F(000) = 596. A total of 5614 reflections were collected in the range of 2.30< q < 25.03? of which 4721 were independent (Rint = 0.0176) and 4159 observed reflections (I ≥ 2s(I)) were used in the refinement. R = 0.0326 and wR = 0.0867. The Mo centre is six-coordinated by four carbonyls (MoC 1.938(4), 2.003(4), 2.019(4), 2.035(4) ) and P, N atoms from the ligand (MoP 2.4812(8), MoN 2.349(3) ?. The coordination geometry of the complex can be described as an octahedron.

The Synthesis and Crystal Structure of the First Trinuclear Molybdenum Complex Containing PyS Ligands [Mo_3(CO)_6(μ-PyS)_2(μ_3-PyS)_2]

The deprotonated derivative pyridine-2-thiolato （PyS-） of pyridine-2-thione （PySH）is a potentially amibidentate or multi-functional donor which coordinates toward transitionmetals with either the exocyclic S or heterocyclic N atom or both atoms to form differentcoordination modes. We have recently reported the synthesis and crystal structure ofthe first dinuclear molybdenum complex with doubly-bridging PyS ligands [Mo2（CO）4（μ-PyS）2（PPh3）2]which was obtained from the reaction of [Mo（CO）3（CH3CN）3]

Hydrothermal Synthesis and Structure of a Novel Binuclear Molybdenum Complex with Oxalate Ligand, (enH_2){NH_4[Co(en)_3][Mo_2O_7(C_2O_4)] }_2·2H_2O

The title complex (enH2){NH4[Co(en)3][Mo2O7(C2O4)]}22H2O (C18H70Co2Mo4- N16O24, Mr = 1396.52) was obtained under hydrothermal conditions and its crystal structure has been determined by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group P21/c with a = 17.8023(8), b = 7.7527(4), c = 16.9781(4) ? b = 103.878(7), V = 2274.8(2) 3, Dc = 2.039 g/cm3, Z = 2, m(MoKa) = 1.878 mm-1 and F(000) = 1408. The final R = 0.0410 and wR = 0.1070 for 4065 observed reflections with I≥2s(I). The crystal structure is composed of bi- nuclear [Mo2O7(C2O4)]4- anions, complex [Co(en)3]2+ cations, protonated ethylenediamine cations, ammonium cations and crystal water molecules, which are held together into a three-dimensional network via hydrogen-bonding interactions. The binuclear structure of [Mo2O7(C2O4)]4- consist of one MoO4 and one MoO6 octahedra through sharing a bridging oxygen atom, where the oxalate ligand acts as a bidentate ligand coordinating to the octahedral molybdenum atom though two deprotonated corboxylate groups.

A dinuclear molybdenum cluster containing i-mnt ligand: synthesis and crystal structure of [Mo_2S_4(i-mnt)_2] (Et_4N)_2

A dinuclear molybdenum(V) cluster compound (Et4N)2[Mo2S4(i-mnt)2] (i-mnt=l,l-dicyanoethylene-2,2-dithiol, (S2C=C(CN)2]2-) has been prepared by the ligand substitution reaction of Mo2S4(iso-pr2dtp)2 (iso-pr2dtp=S2P(OC3H7)2-) with K2(i-mnt) in the presence of Bt4NI. This cluster was characterized by inrrared spectrum, UV-Vis spectrum and single crystal structure analy-sis. The cluster anion [Mo2S4(i-mnt)2]2- possesses C, symmetry with a crystallographic mirror plane through two bridging S atoms. By the S....S supramolecular interactions between two adjacent cluster anions the [Mo2S4(i-mnt)2]2- anions are linked to form infinite chains along the b axis. Crystal data: monoclinic, space group C2/m, a=1.8748(6), b=1.5360(4), c=1.4322(5) nm, ,β=112.02(2)°, V=3.823(4) nm3, Z=4, Dc=1.50 g/cm3. The final R=0.038 and .RW=0.053 for 3015 observed unique reflections.

Structure of Molybdenum Complex of Benzothiazole-2-thiolate（η￣5-C5H5）Mo（CO）2（C7H4NS2）

C14H9NO2S2Mo,Mr=383.29,triclinic,space group P1,a=11.658（4）,b=16.218（8）,c=7.895（3）,a=97.58（4）,β=106.04（3）,γ=85.62（3）°,V=1421（2）,Z=4,Dc=1.79 g/cm￣3,μ=11.81 cm￣（-1）.F（000）=760.Refinement converged to R=0.049 and Rω=0.058 for 3153 independent observed reflections.The compound is a mononuclear molybdenum complex containing benzothiazole-2-thiolato ligand.The molybdenum atom is coordinated by the two carbonyl carbon atoms,tlie cyclopentadienyl carbon atoms,and the nitrogen atom and sulfur atom of benzothiazole-2-thiolate.The coordination polyhedron may be described as a trapezoidal pyramid with the Cp ring centroid as a top.

8-羟基喹啉钼(VI)二氧配合物[MoO_2(C_9H_6NO)_2]的合成、晶体结构及热性能分析

通过X 射线单晶衍射,确定了化合物[MoO2 (C9H6NO)2 ]的晶体结构。化合物晶体属单斜晶系,空间群为C2/c,晶胞参数a=1 .341 6 ( 3 )nm,b= 0. 934 46 ( 19 )nm,c=1 .362 2(3)nm,β=109 .78(3)°,Z=4。该化合物通过Mo原子有一个二重对称轴。在[MoO2 (C9H6NO)2 ]的分子结构中, Mo(VI)原子处于扭曲的八面体中心,N(1)、N(1A)、O(2)、O(2A)位于八面体的赤道位置,O(1)、O(1A)位于八面体的顶点位置。从晶胞堆积图中可看到,通过C(8)—H(8A)…O(1)有一潜在的弱的氢键,使标题化合物的结构更稳定。

“松散”配位的三核钼簇化合物——Mo_3(μ_3-X)(μ-S)_3[S_2P(OEt)_2]_4·L(X=O,S或[(1/2)O+(1/2)S];L=H_2O,SC(NH_2)_2)

文献报道的三钼簇合物大多是配位对称的,而配位不对称的（包括配位空缺或称为配位不饱和的）在化学上更有意义,但报道甚少。最近我们合成了“松散”配位的三核钼簇合物若干个,其中簇合物{Mo3（μ3-S）（μ-S）3[S2P·（OEt）2]4（H2O）}（1）和{Mo3（μ3-X）（μ-S）3[S2P·（OEt）2]4·SC（NH2）2}（2 X=1/2O+1/2S）,已用X射线衍射法测定了晶体结构,发现不对称配位的Mo—L键较通常的长,显得“松散”,配基L可以被其他π-型中性配基置换。

苯甲酸根为桥的双核Eu(Ⅲ)配合物的合成及晶体结构

在EtOH：H2O=2:1的溶剂中，以Eu（NO3）3·6H2O、C6H5COONa和Phen（邻菲哈啉）为原料，合成了四桥双核配合物［Eu2（Phen）2（C6H5COO）6］．晶体属三斜晶系，空间群P1，a=1．08156（7）nm，b=1．19331（7）nm，c=1.24401（8）nm，a=104.972（5）°，β=93．661（5）°γ=113.297（5）°，Z=1．R=0.0437．晶体中2个Eu原子处于晶体学等效位置，配位数为9，Eu-Eu间距离为0．4052nm．讨论了标题化合物的UV－Vis谱与其它Eu3+离子谱的异同．

1,3-丙二胺邻苯二酚钼钨手性八面体配合物的仿生合成、晶体结构以及与ATP作用的液相NMR研究

合成了1,3-丙二胺邻苯二酚钼钨手性八面体配合物(NH3CH2CH2CH2NH2)2[Mo0.4W0.6O2(C6H4O2)2],并对其进行了单晶结构解析,研究了其与ATP作用的液相NMR谱.该晶体属正交晶系,空间群为Pcan.晶胞参数a=0.7501(2)nm,b=2.3994(7)nm,c=1.2178(4)nm,Z=4.[Mo0.4W0.6O2(C6H4O2)2]2-的配位几何构型为手性八面体,晶体为外消旋体.配位阴离子中MoW中心金属离子除了与两个端基O配位形成cis-MO键外,同时还分别与两个邻苯二酚配位基团的的氧原子配位,形成4个M—Ob(M=Mo,W)键,构成两个五元环.利用1HNMR,13CNMR,31PNMR以及1H-15NHMBC对标题配合物及其与ATP在D2O溶剂中的作用进行了研究,发现标题配合物的MoW中心金属离子在纯D2O溶剂中被还原成+5价,但与ATP混合后转化为+6价,且与原配位基邻苯二酚发生解离.解离后的[MO2]2+最大可能与腺嘌呤上的氨基N原子配位,而此配位可能是其抗癌抗肿瘤活性的主要作用机理之一.

氢键在构建超分子[Cu(C_6H_4NO_2)_2(H_2O)_3·H_2O]中的作用

采用水热合成反应,合成了含有多种氢键网络的Cu(Ⅱ)的配合物[Cu(C6H4NO2)2(H2O)3·H2O].对配合物的单晶进行了X光衍射分析.结果表明,在化合物中存在着3种氢键,使化合物晶体构成了无限延伸的三维网络结构,形成了超分子.晶体结构数据:晶体属三斜晶系,空间群为P1,晶胞参数为a=0.69577(5)nm,b=0.71428(10)nm,c=0.86691(6)nm;α=68.3860(12)o,β=68.439(5)o,γ=62.717(3)o,V=0.34554(6)nm3,Z=2,F(000)=193,Dc=1.816g/cm3,最终收敛因子:R=0.0269,ωR=0.0759.讨论了氢键在构建[Cu(C6H4NO2)2(H2O)3·H2O]超分子中所起的作用.并对化合物的红外吸收光谱和紫外可见吸收光谱进行了分析指认.

酰腙配体双氧基钼(Ⅵ)配合物的合成、晶体结构和催化氧化性能（英文）

合成了2个新的单核双氧基钼(Ⅵ)配合物,其分子式通式为[Mo O2L(Me OH)],其中L1和L2分别是N′-(3-溴-2-羟基苯亚甲基)-3,5-二甲氧基苯甲酰肼和N′-(5-溴-2-羟基苯亚甲基)异烟肼的二价阴离子,通过理化手段、光谱方法以及单晶X射线衍射表征了它们的结构。配合物1以单斜晶系P21/n空间群结晶,其晶体学参数a=0.848 98(3)nm,b=2.275 4(1)nm,c=1.069 82(5)nm,β=109.108(1)°,V=1.952 8(1)nm3,Z=4,R1=0.036 7,w R2=0.084 0,S=1.027。配合物2以三斜晶系P1空间群结晶,其晶体学参数a=0.655 05(9)nm,b=1.076 63(7)nm,c=1.303 3(1)nm,α=67.383(2)°,β=84.264(1)°,γ=76.195(2)°,V=0.823 9(1)nm3,Z=2,R1=0.071 3,w R2=0.151 0,S=1.004。X射线分析表明2个配合物中的Mo原子都采取八面体配位构型,配位原子分别来自酰腙配体的NO2给体基团和甲醇氧原子。催化实验表明2个配合物都是有效的烯烃氧化催化剂。

对苯二甲酸二丙炔醇酯与Co_2(CO)_8、Mo_2Cp_2(CO)_4和RuCo_2(CO)_(11)的反应(英文)

室温下对苯二甲酸二丙炔醇酯分别与Co2CO8Mo2Cp2CO4和RuCo2CO11反应得到三个有机金属化合物C6H4pCO2CH2C2Hμ2Co2CO621、C6H4pCO2CH2C2H2RuCo2CO922和HC2CH2OCOC6H4pCO2CH2C2HμMo2Cp2CO43。研究发现三种金属核对端炔氢的屏蔽作用依次为RuCo2CO9>Co2CO6>Mo2CO4Cp2。化合物1的晶体衍射发现属三斜晶系空间群a=8.1392b=8.8083c=11.3433β=96.2606°V=773.443Z=1Dc=1.748g·cm-3R=0.0513wR=0.1266。