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1.
When trinuclear molybdenum cluster compound with "loose coordination site", Mo_3(μ_3-S)(μ-S)_3(μ-dtp)(dtp)_3·H_2O(A) (dtp=diethyldithiophos-phinato anion), is reacted with an excess of imidazole, the H_2O ligand and the bidentate bridging ligand μ-dtp are found to be simultaneously substituted by the imidazole to form the title compound. The title crystal belongs to the space group P(?), Z =2, with the following unit cell parameters: a=14.465(2), b=14.653(4), c=14.886(6), α=99.36(3),β=93.11(2),γ=114.29(2),V=2812(3). The crystalline compound consists of an ordered array of the cluster cation and dtp anion with acetone as packed molecule. The cation possesses a symmetry of C_3. Three Mo atoms form basically an equilateral triangle with three Mo—Mo bond lengths of 2.763 (1), 2.762(1), 2.756(1) respectively. 相似文献
2.
《结构化学》1990,(2)
<正> [Mo3S4(μ-CH3COO)[S2P(OEt)2]3(py)]·(CH3COOCH2CH3) , Mr = 1197. 96,monoclinic,P21/n,a=13. 158(2),b=23. 153(5), c=16. 175(3) A,β = 112. 79(1)°,V=4543. 1(7)A3,Z=4, Dc= 1. 751g/cm-3,λ(MoKa) = 0. 71073A ,μ= 13. 799cm-1,F(000) = 2408. Final R=0. 067 for 4000 reflections. The structure consists of the neutral cluster molecule [Mo3S4(μ-OAc) (dtp)3(py)] (dtp = [S2P(OEt)2]) and the solvent ethyl acetate (AcOEt). The three Mo-Mo bond lengths in the title compound are 2. 691(2) ,2. 747(2) ,2. 762(2) A ,whereas the Mo-N bond length in Mo(3) position is 2. 36(2)A. The important bond lengths of these Mo clusters with (py) ring at the loose coordination site are listed for comparison. 相似文献
3.
The title compound (Mo4XS15P6O12C24H30), α-Mo4XS3(μ-dtp)3(dtp)3 (X=0.6S+0.4O; dtp=-S2P[OEt]2), isolated as a prismatic black crystal, was prepared from ethanolic solution of Mo(CO)6, MoCl5 and P2S5. It crystallizes in triclinic system, space group P with a=14.031(4), b=13.372(2), c=16.270(8)(A), α=92.15(2), β = 72.91(3), γ = 95.20(2)°, V = 2905.4(2)(A)3, Z = 2, Dc = 1.82 g/cm3, Mr=1598.93, F(000)=1564.8, λ=0.71069(A)(MoKα), μ=1.584 mm-1. The final R=0.058, Rw=0.057 for 5016 observed reflections with I≥3.0σ(I). The structure analysis reveals that the title compound has a [Mo4XS3] core, belonging to the cubane-type tetranuclear molybdenum clusters family, with one of its four μ3-caps being statistically occupied by S and O. Three dtp ligands chelated three μ-X capped Mo atoms as terminal ligands, while another three dtp bridged these three Mo atoms and the fourth one, forming an α-type cluster compound. 相似文献
4.
《结构化学》1992,(4)
<正> The title compound was prepared by reaction of Mo3(μ3-O) (μ-S)3-(dtp)4 (H2O) with C6H5COONa and pyridine. C27 H35 Mo3NO9P2S7, Mr = 1091.76, monoclinic, space group P21/c, a = 15. 057(5), b = 13. 052(5), c = 21. 662(6)(?), β=105.97(2)°, V = 4093(2) (?)3, Z = 4, Dc= 1. 77gcm-3, F(000) = 2176, μ(MoKα)=13.50cm-1, final R =0. 068 for 2835 observations. The molecular configuration is new and of approximate C, symmetry, and there are two C6H5COO bridging groups in the structure. The three Mo atoms form an isosceles triangle with three sides of 2. 567(3), 2. 576(3), and 2. 649(3)(?), where the two Mo-Mo bonds bridged by C6H5COO group are much shorter than that without. Something about the reactivity of Mo clusters is discussed. 相似文献
5.
《中国化学快报》1991,(7)
The cluster compound[Mo_4S_4(μ-O_2CC_5H_5)_2(dtp)_4](dtp=S_2P(OEt)_2)wasobtained by the ligand substitution reaction of tetranuclear molybdenum cluster[Mo_4S_4(μ-dtp)_2(dtp)_4]in the mixed solvent of acetone,ethanol and water in thepresence of C_6H_5CO_2Na.It is monoclinic and crystallizes in space group C2/c,Mr=1495.09,a=12.175(5),b=22.01(1),c=20.875(9),β=99.04(4)°;V=5575(5);Z=4;Dc=1.78g/cm~3.Final R factor is 0.066.The result reveals that the[Mo_4S_4]clustercore and t-(dtp)~(-1)ligands are retained and only μ-bridged(dtp)~(-1)ligands aresubstituted by(C_6H_5CO_2)~(-1)in the substitution reaction,thus producing the newtitle cluster compound,the structure of which contains two species of bidentateligand. 相似文献
6.
《结构化学》1992,(2)
<正> The title compound was obtained by the reaction of Mo3(μ3-O) (μ-S)3(dtp)4(H2O) with CH3COONa and pyridine. Mo3C19H38N1O9P3S9,Mr= 1093. 79, triclinic, space group P1, a = 12. 921(3) , b = 14. 260(3) , c= 12. 800(3)(?),α = 97. 54(2), β=116. 66(1), γ=100. 10(2) °, V = 2015, 2(8)(?)3, Z=2, Dc = 1. 80gcm-3, F(000) = 1092, final R = 0. 066 for 3444 observations, room temp. In the structure the three Mo atoms form an isosceles triangle capped by a μ3-O atom with three sides of 2. 589(2) , 2. 642(2), and 2. 627(2) (?) respectively, and the car-boxyl bridged Mo-Mo bond is the shortest one. 相似文献
7.
《结构化学》1990,(3)
<正> The title compound, C24H6oCl5O12P6S26FeMo6,Mr = 2369. 00,crystallized in monoclinic,space group P21/n with cell parameters a= 17. 378(9) ,b=19. 752 (6),c=23. 845(A),β=84. 50(4)°,V = 8133. 4A3,Z=4,Z)c=1.931gcm-3,F(000) = 4676. 00. MoKa radiation (λ=0. 71073A),R=0. 070 for 8403 reflections with I≥3σ(I). The structure was solved by direct methods and showed to consist of an anion Fe-Cl4- and a cluster cation {[Mo3(μ3-S) (S2)3 (dtp)3]2Cl} + which is a double-trinuclear molybdenum cluster formed by sharing a chlorine atom with six weak Cl -S bonds of about 2.936-3. 145A. 相似文献
8.
《结构化学》1993,(2)
<正> The title cluster compound was synthesized by solid state reaction at low heating temperature. C15H30IMo3N3S13, Mr=1083. 93, monoclinic, P21/n, a = 14.396(3), b = 13. 116(3), c=18. 142(8)A;β= 91. 36(3)°; V =3425(2)A3, Z = 4. Dc = 2. 10g/cm3, F(000) = 2112,μ(MoKa) = 27. 29cm-1, final R = 0. 034, Rw = 0. 051 for 1845 unique observed reflections (I≥3σ(I)). The three Mo atoms form an equilateral triangle with an average side length of 2. 714 A. Each Mo atom is coordinated with seven S atoms forming a distorted pentagonal bipyramid. The iodine atom connects with three S atoms (out of the CMo3] plane) with an average distance of 3. 205 A.The title compound has similar cubane-like cluster core [Mo3S7I] as the compound Mo3(μ3-S)(μ2-S2)3(dtp)3I(dtp= (EtO)2PS2). 相似文献
9.
《结构化学》1987,(3)
<正> Mr=2548.12, Triclinic, P1, a=15.941(5), b=15.957(2),c=20.240(6)A, α=76.41(2),β=83.87(2),γ=74.41(2)°,V=4814.6A3, Z=4, Dc=1.757g.cm-3, Final R=0.053 for 11867 reflections. There are two crystallographically independent M1 type trinuclear Mo cluster molecules with 'loose coordination site', A and B, in an asymmetric unit of the title crystal. They are formulated as {Mo3S4(u-dtp)(dtp)3.PhCH2CN}(dtp=[S2P(OEt)2]-) and have essentially identical cluster molecular configuration, but differ from each other in the conformations for the phenyl rings of the ligands PhCH2CN. The lengths of the Mo-Mo bonds are 2.750(1), 2.753(1),and 2.768(1)A for molecule A and 2.742(1), 2.756(1), and 2.764(1)A for molecule B, while the dihedral angles betweem the phenyl ring and the {Mo3} triangle are 25.0° and 94.9° for A and B respectively. 相似文献
10.
SUN Fu-Xia LU Shao-Fang WU Qiang-Jin HUANG Xiao-YingState Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences Fuzhou Fujian China 《中国化学》1997,15(5):417-424
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. 相似文献
11.
[Mo3,OS3(dtp)4(H2O)] reacts with NaOAc·3H2O in Py to give the title compound. The crystal data are as follows: [Mo2OS3)(OAc)2(dtp)2·Py]?0.5H,O(dtp = [S3P(OC2H5)2]?, Py = C5H5N); M = 976.64; triclinic; space group P1 ; a=11.704(5), b=14.169(7), c= 11.688 (5) Å α=109.94(4) β = 91.53(4), γ = 91.93(4)°; V= 1819(1) Å2; Z=2; Dc = 1.78 g·cm?3 λ(Mo Kα) = 0.71069 Å μ=15.15 cm?1; F(000) = 970 T=296 K; final R=0.071 for 1652 reflections with I>3σ(I). In the molecule, the [Mo3OS3] core is surrounded by two bridging OAc groups and two terminal chelate dtp groups attached to the {Mo3} triangle in a symmetric style, and the Py ligand is coordinated to the Mo atom at the apex of {Mo3} triangle with the nitrogen. This novel configuration is obtained for the first time with Mo—N bond length being 2.27 (2) Å and three Mo—Mo bond lengths 2.584 (4), 2.587 (4) and 2.657(4) Å, respectively. As a whole, the molecule has a virtual C2 symmetry. 相似文献
12.
The reaction of trinuclear molybdenum cluster {Mo3S4(μ-dtp) (dtp)3 (H2O)} 1 [dtp= S2P(OEt)2] with RCO2Na (R?H, CH3) in the presence of Py gave the black compounds {Mo3S4 {μ-O2 CR) (dtp)3 (Py)} (2, R?H, 3, R?CH3). Both compounds are characterized by X-ray crystallography. It is shown that crystals 2 and 3 belong to space group P&1bar; with Z=2 and a=10.519(2), b= 12.121(2), c=15.757(2)Å, α=93.27(1), β=94.63(1), γ = 105.22(1)°, V= 1925 Å3 for crystal 2, whereas a=9.556 (2), b=14.067(7), c=15.914 (9) Å, α=101.41 (4), β=101.44(4), γ-74.26(3)°, V=1994Å3 for crystal 3. The final R factors are 0.041 and 0.048 for crystal 2 and 3 respectively. The structure analysis indicates that (O2CR)? ligand selectively substitutes the bridging (dtp) ligand. This type of Mo, cluster molecule where structure contains two species of bidentate ligand is for the first time to be obtained by us. 相似文献
13.
The title compound was prepared by the reaction of Mo_3S_4(dtp)_4(H_2O)[ctp=S_2P(OEt)_2]with NaOAc·3H_2O and C_4H_8NCS_2NH_4.Crystallographic data:[Mo_3(μ_3-S)(μ-S)_2(μ-OAc)-(S_2CNC_4H_8)_3(O)_2]·0.5CH_2CI_2·2H_2O,Mr=980.18,triclinic,space group P,α=12.360(3),b=16.653(6),c=9.206(2)A,α=101.97(2),β=108.32(2),γ=86.14(3)°.V=1759.6(9)A~3,Z=2,Dc=1.85 g/cm~3,F(000)=962,μ(Mo K_α)=16.53 cm~(-1).Final R=0.044 for 4301 reflections with I≥3σ(I).This compoundmay be regarded as a mixed-valent trinuclear molybdenum cluster{Mo_2(V)Mo(Ⅳ)(μ_3-S)(μ-S)_2-(μ-OAc)(S_2CNC_4H_8)_3(O)_2}.The Mo-Mo distances are 2.783(1),2.833(1)and 3.374(2)A in the Mo_3non-equilateral triangle and there exist only two Mo-Mo bonds.The cluster was obtained by oxi-dation and ligand substitution of{Mo_3(μ_3-S)(μ-S)_3[μ-S_2P(OEt_2)][S_2P(OEt)_2]_3(H_2O)}. 相似文献
14.
Title compound, Mr =1273.16, was synthesized by a substitution reaction and its crystal is triclinic belonging to space group P1 with cell parameters: a =13.944(2), b =14.143(7), c =14.233(3) Å, α =77.35(3)°, β =69.94(2)°, γ =63.50(3)°, V=2351(1) Å3, Z=2, Dc =1.799g cm?2. Room temperature, graphite-filtered Mo Kα radiation (λ =0.71073Å) was used for data collection. μ =14.988 cm?1, F(000) =1280, R=0.051 for 7025 observed reflections. The crystal consists of decrete cluster molecules containing a cluster core [Mo2(μ3-S)]10+ with three μ-S, one μ-dtp(dtp =[S2P(OC2H5)]2-), three χ-dtp and one allylthioureo to form a local six-coordinated sphere around each Mo atom. The bonds of cluster skeleton [Mo3(μ3-S)(μ-S)3]4+, Mo? Mo 2.744~2.766, Mo—(μ2-S) 2.340~2.342 and Mo—(μ-S)2.272~2.296 Å, are comparable with those found in the related analogues. 相似文献
15.
Jian-Quan Huang Shao-Fang Lu Xiao-Ying Huang Qiang-Jin Wu Rong-Min Yu 《Journal of Cluster Science》1997,8(1):47-57
The synthesis and crystal structure of the first example for hybrid Sn-Mo tetranuclear cubane-like cluster compound containing S/O mixed triple capping atom [Mo3(SnBr3)(μ 3-O)(μ 3-S)3(dtp)3(py)3]·(CH2Cl2) (A) (dtp=S2P(OC2H5)2) are reported. The compound is prepared by the reaction of [Mo3(μ 3-O)(μ-S)3(dtp)4·(H2O)] with SnBr 3 ? . The molecular structure of the cluster can be described as a [Mo3OS3] core with the SnBr 3 ? fragment linked to {Mo3} triangle by three (μ 3-S). Three Mo-Mo bond lengths are 2.616(2), 2.620(2), 2.628(2) Å, respectively, and the molecule has approximately C3v symmetry. There is no bonding between Sn and Mo atoms, however, the addition of SnBr 3 ? may cause electron transfer from Sn2+ to [Mo3OS3] core to result in the shortening of Mo-Mo bond distances. The compound crystallizes in the monoclinic space group P21/n with refined lattice parameters ofa=13.012(4),b=22.877(6),c=18.585(6) Å,β=96.34(3)°,V=5498(3)Å3, andZ=4. Full matrix refinement converged with final agreement factor ofR=0.054,R w=0.064. 相似文献
16.
Shao-Fang Lu Ying Peng Hong-Jun Fan Qiang-Jin Wu Zi-Xiang Huang Jian-Quan Huang 《Journal of Cluster Science》2002,13(1):15-31
Three new heterometallic tetranuclear cluster compounds with a [Mo3YS3M] cubane-like cluster core (M=Cu, Pb, Sb; Y=O, S), [Mo3OS3(CuI)(-OAc)2(dtp)2(DMF)] (1), (dtp=S2P(OC2H5)–
2), [Mo3OS3(PbI3)(dtc)3(py)3] (2) (dtc=S2CN(C2H5)–
2), [Mo3S4(SbI3)(dtcpyr)4(py)]·2H2O (3) (dtcpyr=S2CNC4H–
8) have been synthesized and structurally characterized by IR, Raman, UV–Vis, 1H NMR, 13C NMR spectroscopies and single-crystal X-ray diffraction studies. Their structure and bonding features are discussed. Compounds 1 and 2 show a good third-order optical nonlinearity, as measured by degenerate four-wave mixing technique. 相似文献
17.
The Electron Transfer Series [MoIII(bpy)3]n (n=3+, 2+, 1+, 0, 1−), and the Dinuclear Species [{MoIIICl(Mebpy)2}2(μ2‐O)]Cl2 and [{MoIV(tpy.)2}2(μ2‐MoO4)](PF6)2⋅4 MeCN
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Dr. Mei Wang Dr. Thomas Weyhermüller Prof. Karl Wieghardt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(29):9037-9044
The electronic structures of the five members of the electron transfer series [Mo(bpy)3]n (n=3+, 2+, 1+, 0, 1?) are determined through a combination of techniques: electro‐ and magnetochemistry, UV/Vis and EPR spectroscopies, and X‐ray crystallography. The mono‐ and dication are prepared and isolated as PF6 salts for the first time. It is shown that all species contain a central MoIII ion (4d3). The successive one‐electron reductions/oxidations within the series are all ligand‐based, involving neutral (bpy0), the π‐radical anion (bpy.)1?, and the diamagnetic dianion (bpy2?)2?: [MoIII(bpy0)3]3+ (S=3/2), [MoIII(bpy.)(bpy0)2]2+ (S=1), [MoIII(bpy.)2(bpy0)]1+ (S=1/2), [MoIII(bpy.)3] (S=0), and [MoIII(bpy.)2(bpy2?)]1? (S=1/2). The previously described diamagnetic dication “[MoII(bpy0)3](BF4)2” is proposed to be a diamagnetic dinuclear species [{Mo(bpy)3}2(μ2‐O)](BF4)4. Two new polynuclear complexes are prepared and structurally characterized: [{MoIIICl(Mebpy0)2}2(μ2‐O)]Cl2 and [{MoIV(tpy.)2}2(μ2‐MoVIO4)](PF6)2?4 MeCN. 相似文献
18.
Kentaro Takano Hideki Kawasaki Genta Sakane Takashi Shibahara 《Journal of Cluster Science》2007,18(3):684-696
The reaction of a sulfur and oxygen-bridged 8-quinolinolato trinuclear molybdenum cluster [Mo3OS3(qn)3(H2O)3]+ (3; Hqn = 8-quinolinol) with equimolar amounts of acetylene carboxylic acid, 4-pentynoic acid, 5-hexynoic acid, acetic acid,
and pimelic acid gave clusters having μ-carboxylato groups, [Mo3OS3(qn)3(H2O)(μ-HC≡CCOO)] (6), [Mo3OS3(qn)3(H2O)(μ-HC≡C(CH2)2COO)] (7), [Mo3OS3(qn)3(H2O)(μ-HC≡C(CH2)3COO)] (8), [Mo3OS3(qn)3(H2O)(μ-CH3COO)] (4), and [{Mo3OS3(qn)3(C2H5OH)}2(μ-C7H10O4)] (5), respectively. X-ray structural analyses, 1H NMR, and electronic spectra of these clusters made clear that each of the COO− groups of the reagents bridges two Mo atoms in each cluster and that no adduct formation occurred at the sulfurs in the clusters.
The reaction of 3 with a large excess-molar amount (50 times) of acetylene carboxylic acid gave [Mo3OS(μ3-SCH=C(COOH)S)(qn)3(H2O)(μ-HC≡CCOO)] (9) with two molecules of acetylene carboxylic acid, one acting as a carboxylato bridge and the other in adduct formation, as
supported by the electronic and 1H NMR spectra. The corresponding aqua cluster [Mo3OS3(H2O)9]4+ (1), on the contrary, reacts with acetylene carboxylic acid to give adduct [Mo3OS(μ3-SCH=C(COOH)S)(H2O)9]4+ (2).
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
19.
Shao-Fang Lu Jian-Quan Huang Zhi-Da Chen Qiang-Jin Wu Wen-Zhang Chen Xiao-Ying Huang Zi-Xiang Huang Jin-Ling Huang Jia-Xi Lu 《Journal of Cluster Science》1992,3(2):179-199
By the reaction of cluster [Mo3OS3](dtp)4(H2O) used as starting material with CuI using [3+1] mode, two novel heterometallic-heterobridging cubane-type tetranuclear cluster compounds [CuMo3OS3]·I·(-OAc)[S2P(OC2H5)2]3·L [(I)L=py, (II)L=DMF] [dtp=S2P(OC2H5)2; OAc=OOCCH3] containing [CuMo3OS3] core have been obtained. Compounds (I) and (II) have been characterized by IR, EPR, UV-VIS, electrochemistry and X-ray crystallography. By comparison of these two compounds with the analogous [CuMo3S4] series in the structure and molecular orbital calculation, the influence of mixed S/O bridging on the structure is discussed. It is demonstrated that the {Mo3S3} cluster ring in [Mo3OS3]4+ possesses a similar quasi-aromaticity to [Mo3S4]4+. Crystal data: for (I), space group=
,a=13.781(8)Å,b=14.523(6)Å,c=12.098(6)Å, =98.37(4)°, =109.41(5)°, =105.00(5)°,V=2133(2)Å3,Z=2,R=0.058; for (II), space group=
,a=13.215(4)Å,b=17.818(8)Å,c=9.873(4)Å, =106.06(4)°, =109.78(3)°, =82.00(3)°,V=2100(2)Å3,Z=2,R=0.045.Invited Professor at Fuzhou University. 相似文献