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The trinuclear Mo cluster [Mo3(3–X)(2–Se2)3{S2P-(OEt)2}3]Cl (X=0.65S+0.35Se) (1) has been synthesised by reacting MoCl3·3H2O with ZnSe and [Me4N][S2P(OEt)2] in an EtOH/HCl medium. Reduction of (1) by Ph3P in the presence of [Me4N]-[S2P(OEt)2] and pyridine gave [Mo3(3–X)(2–Se)3 {S2P(OEt)2}4(py)] (X=0.65S+0.35Se, py=C5H5N) (2). Complex (2) was, in turn, converted into [Mo3(3–X)(2–SeS)3{S2P(OEt)2}3]I (X=0.65S+0.35Se) (3) by treatment with H2S and I2. The structures of complexes (1), (2) and (3) were established by X-ray crystallography. 相似文献
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V. V. Sharutin I. V. Egorova O. K. Sharutina O. A. Dorofeeva T. K. Ivanenko A. V. Gerasimenko M. A. Pushilin 《Russian Journal of Coordination Chemistry》2004,30(12):874-883
The reactions of tetraphenylbismuthonium and -stibonium salts Ph4EX (E = Bi, Sb; X = I, OSO2 (C6H3(CH3)2-2,5), OSO2C6H3(OH-4)(COOH-3)) with bismuth triiodide in acetone afford complexes [Ph4Bi]+[PhBi(C5H5N)I3]-, [(Ph4BiO)2S(O){2,5-(CH3)2C6H3S(O)} [Ph2Bi2I6]2–, [Ph4Sb [Bi4I16]4-·2(CH3)2C=O, and [Ph4Sb] 3+ + [Bi5I18]3-, whose structural units, according to the X-ray diffraction data, are tetraphenylbismuthonium (-stibonium) cations and mono-, di-, tetra-, and pentanuclear anions, respectively. 相似文献
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《Journal of organometallic chemistry》2003,665(1-2):205-213
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根据配合物H2C[P(Ph)2AUX]2(X=I,CI)和HC[P(Ph)2AUX]3(X=I,CI)的晶体结构对它们进行了从头算研究,在MP2近似水平下得到绕C-P旋转所产生构象的势能曲线,从而揭示AU(I)-AU(I)相互作用. 计算结果表明,在所研究的四个配合物中均存在AU(I)-AU(I)相互作用,该作用较弱,约为10. 0~16. 5kJ/mol,与Schmibaur的实验估计值和Pyykko等对其它模型配合物的计算结果接近. 相似文献
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Rajendra Singh Dhayal Kiran Kumar Varma Chakrahari V. Ramkumar Sundargopal Ghosh 《Journal of Cluster Science》2009,20(3):565-572
Abstract Reaction of [(η5-C5Me5Mo)2B5H9], 1 with 5-fold excess of n-BuLi at −70 °C followed by excess of RI (R = n-Bu or Ph) at room temperature yielded B-R inserted metallaboranes [(η5-C5Me5Mo)2B5H8R] (2: R = n-Bu, 5: R = Ph), [(η5-C5Me5Mo)2B5H7R2] (3, 4: R = n-Bu; 6, 7: R = Ph). Isolated yields of mono-alkyl/arylated species are better than di-alkyl/arylated ones. All the new cluster compounds have been characterized by IR, 1H, 11B, 13C NMR and mass spectroscopy as simple substitution derivatives of [(η5-C5Me5Mo)2B5H9] and the structural types of one of these species, 2 was established by X-ray crystallographic analysis.
Graphical Abstract Reaction of [(η5-C5Me5Mo)2B5H9], with 5-fold excess of n-BuLi at −70 °C followed by excess of RI (R = n-Bu or Ph) at room temperature yielded B-R inserted metallaboranes [(η5-C5Me5Mo)2B5H9-nRn] (When R = n-Bu, n = 2, 1; R = Ph, n = 2, 1).
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《Chemical physics letters》1987,135(6):525-528
The pressure shifts of the first three bands appearing in the visible spectra of [Pt3(CO)6]2−n (n = 3–5) have been measured in solution over the range 0–10 kbar. Previous electronic calculations performed on the dimer in conjunction with these results afford a possible set of assignments for the first three bands appearing in the visible spectrum for the dimer. 相似文献
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用Co2(CO)8分别与两个杂环配体C(S)NHP(S) (C6H4OCH3)OC(Ph)CH (L1)和C(S)NHC(CH3)2P(S) (CI)N(Ph) (L2)反应.合成两个新的三核钴羰基硫簇合物Co3(CO)7(μ3-S) [μ,η2-CNP(S) (C6H4OCH3)OC(Ph)CH] (Ⅰ)和Co3(CO)7(μ3-S) [μ,η2-SCNC(CH3)2P(S) (CI) N(Ph)] (Ⅱ).用元素分析,IR,1H NMR,31P NMR 及 MS谱表征了它们的结构,同时用X射线衍射法测定了它们的晶体分子结构,二者属于三斜晶系,P1空间群,I的晶胞参数为:a=0.84768(1)nm,b=1.19049(3)nm,c=1.43639(1)nm,α=86.926(1)°,β=81.60l(3)°,γ=88.535(2)°,V=1.4318(5)nm3,Z=2,Dc=1.641g@em-3,F(000)=716,μ=1.893mm-1,R=0.0602,Rw=0.1515.Ⅱ的晶胞参数为:a=1.2050(2)nm,b=1.2448(2)nm,c=0.8951(2)nm,α=97.49(1)°,β=93.552(4)°,γ=108.432(3)°,V=1.2554(3)nm3,Z=2,Dc=1.84lg@cm-3,F(000)=690,μ=2.419mm-1,R=0.0423,Rw=0.1075.Ⅰ和Ⅱ的分子骨架Co3S为三角锥构型,S作为面桥基配体,所有C0作为端基配体与三个Co原子成键.I中含有CoCoCN四元环组件,Ⅱ中含有CoCoSCN五元环组件. 相似文献
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Rainer Bartsch Christian Müller Axel Fischer Peter G. Jones 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract Syntheses and structures of penta- and hexaphosphorus analogues of ferrocene have been described recently1. Unlike their simple ferrocene analogues, these complexes have further ligating potential towards other transition metal centres by virtue of the availability of the ring phosphorus lone-pair electrons that are not involved in the η5-coordination. We now describe the first examples of coordination compounds of the triphospha-ferrocene [Fe(η5-C5Me5) (η5-C2 tBu2P3]. In the ruthenium complex [Fe(η5-C5Me5)(η5-C2 tBu2P3) Ru3(CO)9] 2 two adjacent phosphorus atoms of the η5-C2 tBu2P3 ring are interlinked by a ruthenium carbonyl cluster in which all three ruthenium atoms interact with the phosphorus atoms. The tetrametallic nickel complex [Fe(η5-C5Me5)(η5-C2 tBu2P3)Ni(CO)2]2 3 represents the first example of intermolecular interlinkage of two phospha-ferrocene systems by two metal centres. 相似文献
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Rainer Bohlen Gerd-Volker Röschenthaler 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):483-486
Abstract The properties of PF5, HPF4, H2PF3, and H3PF2 (Δ5[sgrave]5P derivatives of (HO)3PO, (HO)2HPO, (HO)H2PO, and of the hypothetic H3PO) and the formation of the related Δ5[sgrave]6P anions PF6 –, HPF5 –, and trans-H2PF4 – have been studied some years ago 1–4. The mono and spirocyclic dioxa and tetraoxa analogues, 1 and 2 available from the corresponding precursor phosphoranes by fluoride addition could be found also as products in the reaction of phosphite 35 and K+(CF3)2CFO– together with two other phosphates, 4 and 5. A 19F–19F homocorrelated 2 D NMR spectrum of 2 indicated coupling of the P–F fluorine nuclei with two CF3 groups by a non bond mechanism. 相似文献
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Jain A Reback ML Lindstrom ML Thogerson CE Helm ML Appel AM Shaw WJ 《Inorganic chemistry》2012,51(12):6592-6602
A series of dipeptide substituted nickel complexes with the general formula, [Ni(P(Ph)(2)N(NNA-amino acid/ester)(2))(2)](BF(4))(2), have been synthesized and characterized (P(2)N(2) = 1,5-diaza-3,7-diphosphacyclooctane, and the dipeptide consists of the non-natural amino acid, 3-(4-aminophenyl)propionic acid (NNA), coupled to amino acid/esters = glutamic acid, alanine, lysine, and aspartic acid). Each of these complexes is an active electrocatalyst for H(2) production. The effects of the outer-coordination sphere on the catalytic activity for the production of H(2) were investigated; specifically, the impact of sterics, the ability of the side chain or backbone to protonate and the pK(a) values of the amino acid side chains were studied by varying the amino acids in the dipeptide. The catalytic rates of the different dipeptide substituted nickel complexes varied by over an order of magnitude. The amino acid derivatives display the fastest rates, while esterification of the terminal carboxylic acids and side chains resulted in a decrease in the catalytic rate by 50-70%, implicating a significant role of protonated sites in the outer-coordination sphere on catalytic activity. For both the amino acid and ester derivatives, the complexes with the largest substituents display the fastest rates, indicating that catalytic activity is not hindered by steric bulk. These studies demonstrate the significant contribution that the outer-coordination sphere can have in tuning the catalytic activity of small molecule hydrogenase mimics. 相似文献
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M. S. Grigor’ev N. A. Budantseva A. M. Fedoseev 《Russian Journal of Coordination Chemistry》2013,39(1):87-95
Two series of isostructural double An(IV) and guanidinium carbonates were obtained as single crystals of the formula [C(NH2)3]6[An(CO3)5] · nH2O (An = Th, U, Np, and Pu; n = 3 (I) and 4 (II)) and examined by X-ray diffraction. For the Pu(IV) complexes, a = 10.490(2) Å, b = 33.798(5) Å, c = 10.519(2) Å, β = 119.414(7)°, space group P21/c, Z = 4, R = 0.0369 (I) and a = 16.0895(18) Å, b = 13.1458(14) Å, c = 16.6951(18) Å, β = 108.116(6)°, space group C2/c, Z = 4, R = 0.0171 (II). Both series of complexes contain the anions [An(CO3)5]6?, in which the An atom is coordinated to five chelating bidenate carbonate ions. The coordination polyhedra of the An atoms are distorted bicapped square antiprisms. Within both the series, the An-O bond lengths decrease monotonically only for the sequence Th-U-Np. The average Np-O and Pu-O bond lengths in both tri- and tetrahydrates are virtually equal. The IR and electronic absorption spectra of the complexes obtained were studied. The absorption bands due to the f-f transitions experience bathochromic shifts in the spectra of the U4+ and Pu4+ carbonate complexes and hypsochromic shifts in the spectra of the Np4+ complexes. 相似文献
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《Journal of organometallic chemistry》1986,299(2):169-178
The complex cations [C5H5Fe(CO)2L]BF4 (L = (C6H5)3−nP(NR2)n; n = 0−3 R = CH3, C2H5) have been obtained from the reaction of [C5H5Fe(CO)2THF]BF4 (I) with L. The reaction of I with E(NR2)3 (E = As, Sb; R= CH3) is also described. Spectroscopic investigations (IR, 1H, 13C and 31P NMR) indicate an increase in electron density on the iron center through increase of the number of P-bound NR2 groups. 相似文献
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V. V. Sharutin V. S. Senchurin O. K. Sharutina B. B. Kunkurdonova A. G. Burlakova 《Russian Journal of Inorganic Chemistry》2011,56(8):1264-1271
Complexes with antimony-containing anions, [Ph3MeP] + 2 [SbI5]2? (I), [Ph3MeP] + 2 [Sb3I12]3? (II), [Ph3MeP] + 3 [Sb3I12]3? · Me2C=O (III), and [Ph3MeP] + 3 [Sb2I9]3? (IV), were synthesized by reacting triphenylmethylphosphonium iodide with antimony iodide. The central atom in the cations of the complexes has a distorted tetrahedral coordination. In the trinuclear anions of complexes II and III, each of the terminal SbI3 groups is bound to the central Sb atom through two μ2- and one μ3 iodine bridges (SbSbSb angles are 103.0° and 102.2°, respectively). In the binuclear anion of complex IV, antimony atoms are linked with each other via three bridging iodine atoms. 相似文献
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V. V. Sharutin I. V. Egorova O. K. Sharutina E. A. Boyarkina 《Russian Journal of Coordination Chemistry》2008,34(6):461-465
The complexes [Ph3PMe] 2 + [BiI5]2? (I) and [Ph3PMe] 2 + [BiI5 · C 5H5N]2? · C 5H5N (II) were synthesized by the reaction of bismuth triiodide with triphenylmethylphosphonium iodide, and their structures were determined by X-ray diffraction analysis. The P atom in cation I has slightly distorted tetragonal coordination polyhedron (the CPC angles 109.42(4)° and 109.52(4)°, the bond lengths P-CPh 1.779(2), P-CMe 1.793(1) Å. The Bi atom in the anion of complex I has an ideal trigonal-bipyramidal coordination polyhedron (Bi-Ieq 3.0031(4), Bi-Ieq 3.0485(5) Å). The crystal of complex II consists of the anions [BiI5 · C 5H5N]2?, solvated pyridine molecules, and two types of crystallographically independent tetrahedral triphenylmethylphosphonium cations (the angles CPC 106.9(1)°–111.7(1)°, the distances P-CPh 1.785(3)–1.792(3), P-CMe 1.793(3), 1.786(3) Å). The Bi atoms in the anion of complex II have a distorted octahedral coordination polyhedron (Bi-I 3.0878(4)–3.1240(3), Bi-N(1) 2.628(3) Å). 相似文献
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《Journal of Coordination Chemistry》2012,65(24):4363-4370
Two new complexes containing M(II) ammine cations (M = Ni, Cd) and octahedral rhenium(III) thiocyanoammine and thiocyanohydroxoammine cluster anions, [Ni(NH3)6][Re6S8(CN)4(NH3)2]?2H2O (1) and [Cd(NH3)6][{Cd(NH3)5}{Re6S8(CN)4(OH)(NH3)}]2?5H2O (2), have been synthesized by hydrothermal reactions starting from Cs1.83K2.17[Re6S8(CN)4(OH)2]?2H2O. The compounds were structurally characterized by single-crystal X-ray diffraction analysis, elemental analysis, energy dispersive spectroscopy, and IR spectroscopy. Both compounds adopt monoclinic crystal structures composed from discrete ionic species which are held together by multiple hydrogen bonds between CN–, OH–, and NH3 ligands and lattice water. 2 consists of {Cd(NH3)5}2+ attached to the OH group of the [Re6S8(CN)4(OH)(NH3)]3– cluster anion via the Re–OH–Cd linkage. 相似文献
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Jean Bernard Ballif Pierre Braunstein Andrew D. Burrows Richard D. Adams Wengan Wuz 《Journal of Cluster Science》1994,5(3):443-466
The reaction of the ketophosphine ligand Ph2PCH2C(O)Ph (P~O) with [PtCl2(NCMe)2] and carbon monoxide in THF in the presence of an excess of zinc afforded the 70 electron pentanuclear cluster [Pt5(CO)(μ-CO)5(P~O)4] (1). Reaction of the palladium(0) complex [Pd2(dba)3] CHCl3 (dba = dibenzylideneacetone) with Ph2PCH2C(O)R [R = Ph or C5H4Fe(C5H5)] under SO2 led to the pentapalladium cluster compounds [Pd5(μ3-SO2)2 (μ-SO2)2 {Ph2PCH2C(O)R}5] (2a,R = Ph;2b,R = C5H4Fe(C5H5)), Cluster (1) reacts with 2,6-xylyl isocyanide, CNC6H3Me2-2,6 to give a red cluster of formula [Pt5(μ-CNC6H3Me2-2, 6)3 (CNC6H3Me2-2, 6)5 (P~O)2] (3) and a green complex (4). The corresponding complexes (6) and (7) were also obtained by using PPh3 instead of P~O. Clusters (2a) and (2b) react with [NEt3Bz] Cl to give[NEt3Bz][Pd3(μ-SO2)2 (μ-Cl){Ph2PCH2C(O)R}3](8a,R = Ph;8b,R = C5H4Fe(C5H5)). The molecular structures of (1) and (3) were determined by single-crystal X-ray diffraction analyses. 相似文献
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Introduction1,4 Diazabicyclo[2 .2 .2 ]octane (DABCO)wasre portedtocatalyzeorganicreactionsduetoitsstrongbasici ty .1,2 Severalchiraltrans 2 ,3 disubstitutedDABCOshavebeensynthesizedandappliedtotheasymmetricBaylis Hillmanreaction3andvicinalhydroxylation .4ThefirstsynthesisofthetitlecompoundwasreportedbySoai5from (2S ,5S) bis(phenylmethyl)piperazine (1) ,asshowninScheme 1.Butthisprocedureislengthy ,andtheoverallyieldisnotsosatisfactory .Besides ,thereport edmethodforthepreparationof 1is… 相似文献