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1.
The 8,9′-[closo-{3-Co(η5-C5H5)-1,2-C2B9H10}]2 (1) species, in which two large closo-CoC2B9 sub-clusters are connected by a B-B bond, is unexpectedly obtained from the reaction of closo-[3-Co(η5-C5H5)-1,2-C2B9H11] with sulfur in the presence of aluminium chloride under reflux conditions. The solid state conformation of 1 seems to be the result of a pair of intramolecular C-H?H-B dihydrogen bonds between the protonic H atoms of the C5H5 fragment of a sub-cluster and the hydridic H atoms of the C2B9H11 fragment in the other sub-cluster in 1.  相似文献   

2.
The hitherto unknown indenyl-derived ylide, methyldiphenylphosphonium 1-indenylide, 1-C9H6PMePh2 (1) and its chromium(0) complex, Cr(η5-1-C9H6PMePh2)(CO)3 (2) have been synthesized and characterized spectroscopically and crystallographically. The structures and properties of 1 and 2 are compared with those of the analogous C5H4PMePh2 and its chromium complex, Cr(η5-C5H4PMePh2)(CO)3. Compound 2, obtained as a racemic mixture, exhibits planar chirality resulting from coordination of the prochiral aromatic ligand.  相似文献   

3.
The structures of the metallacarborane cations [(-9-Me2S-7,8-C2B9H10)Ni(-Cp)Ni(-9-Me2S-7,8-C2B9H10)]+ (2) and [Cp*Ru(Me2S-C2B9H10)RuCp*]+ (4b) were established by X-ray diffraction analysis. These results confirmed the triple-decker structure proposed for complex 2 earlier, whereas complex 4b proved to be 13-vertex dimetallacarborane rather than the triple-decker complex, as has been suggested earlier.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1879–1883, September, 2004.  相似文献   

4.
Visible light irradiation of the benzene complex [(η-1-ButNH-1,7,9-C3B8H10)Fe(η-C6H6)]+ in the presence of the charge-compensated carborane anions [9-L-7,8-C2B9H10] (L = SMe2, NMe3) affords ferracarboranes (η-1-ButNH-1,7,9-C3B8H10)Fe(η-9-L-7,8-C2B9H10). Their structures were established by X-ray diffraction analysis.  相似文献   

5.
With copper(I) iodide as catalyst, σ-alkynyls, compounds (η5-C5H5)Cr(NO)2(CC-C6H5) (5), [(η5-C5H4)-COOCH3]Cr(NO)2(CC-C6H5) (10), and [(η5-C5H4)-COOCH3]W(CO)3(CC-C6H5) (13), were prepared from their corresponding metal chloride 1, 6 and 12. Structures of compound 3, 5 and 12 have been solved by X-ray diffraction studies. In the case of 5, there is an internal mirror plane passing through the phenylethynyl ligand and bisecting the Cp ring. The phenyl group is oriented perpendicularly to the Cp with an eclipsed conformation. The twist angle is 0° and 118.4° for -CC-Ph and two NO ligands, respectively. The orientation is rationalized in terms of orbital overlap between ψ3 of Cp, dπ of Cr atom, and π of alkynyl ligand, and complemented by molecular orbital calculation. The opposite correlation was observed on the chemical shift assignments of C(2)-C(5) on Cp ring in compounds 6 and 12, using HetCOR NMR spectroscopy. The electron density distribution in the cyclopentadienyl ring is discussed on the basis of 13C NMR data and compared with the calculations via density functional B3LYP correlation-exchange method.  相似文献   

6.
The cyclopentadienylchromium carbonyl thiocarbonyls Cp2Cr2(CS)2(CO)n (n = 4, 3, 2, 1) have been studied by density functional theory using the B3LYP and BP86 functionals. The lowest energy Cp2Cr2(CS)2(CO)4 structure can be derived from the experimentally characterized unbridged Cp2Cr2(CO)6 structure by replacing the two terminal carbonyl groups furthest from the Cr-Cr bond with two terminal CS groups. The two lowest energy Cp2Cr2(CS)2(CO)3 structures have a single four-electron donor η2-μ-CS group and a formal Cr-Cr single bond of length ∼3.1 Å. In contrast to the carbonyl analogue Cp2Cr2(CO)5 these Cp2Cr2(CS)2(CO)3 structures are viable with respect to disproportionation into Cp2Cr2(CS)2(CO)4 and Cp2Cr2(CS)2(CO)2 and thus are promising synthetic targets. The lowest energy Cp2Cr2(CS)2(CO)2 structures have all two-electron donor CO and CS groups and short CrCr distances around ∼2.3 Å suggesting the formal triple bonds required to give the chromium atoms the favored 18-electron configurations. These Cp2Cr2(CS)2(CO)2 structures are closely related to the known structure for Cp2Cr2(CO)4. In addition, several doubly bridged structures with four-electron donor η2-μ-CS bridges are found for Cp2Cr2(CS)2(CO)2 at higher energies. The global minimum Cp2Cr2(CS)2(CO) structure is a triply bridged triplet with a CrCr triple bond (2.299 Å by BP86). A higher energy singlet Cp2Cr2(CS)2(CO) structure has a shorter Cr-Cr distance of 2.197 Å (BP86) suggesting the formal quadruple bond required to give each chromium atom the favored 18-electron configuration.  相似文献   

7.
Volatile mixed-ligand complexes of Zn(i-Bu2PS2)2 with Phen and 2,2-Bipy have been synthesized. The crystal structures of the complexes ZnPhen{(i-C4H9)2PS2}2 and Zn(2,2-Bipy){(i-C4H9)2PS2}2 were determined by single crystal X-ray diffractometry (CAD-4 diffractometer, MoK radiation, 2100 Fhkl, R = 0.0423 for the first complex and 2003 Fhkl, R = 0.0486 for the second). The crystals are monoclinic with cell dimensions a = 17.580(4), b = 9.969(2), c = 19.175(4) , = 90.33(3)°, V = 3360(1) 3, Z = 4, d calc = 1.313 g/cm3, space group P2/n (for the Phen complex); a = 24.219(5), b = 11.386(2), c = 24.916(5) , = 97.70(3)°, V = 6809(2) 3, Z = 8, d calc = 1.249 g/cm3, space group C2/c (for the 2,2-Bipy complex). The complexes are constructed from discrete monomer molecules. The coordination polyhedra of the Zn atoms are distorted tetrahedra formed by two S atoms of the two monodentate i-Bu2PS 2 - ligands and two N atoms of the cyclic bidentate Phen or 2,2-Bipy molecules. Intermolecular interactions and packings in the structures are analyzed.  相似文献   

8.
The pressure dependences (dν/dP) of the main IR and Raman bands of Zeise’s complexes, K[Pt(η2-C2H4)Cl3] and [Pt(η2-C2H4)Cl2]2, have been determined for the first time for selected pressures up to ∼33 kbar with the aid of diamond-anvil cells. Neither complex undergoes a pressure-induced structural change throughout the pressure range investigated. The dν/dP values range from −0.13 to 0.79 cm−1 kbar−1. The negative values have proved particularly informative in identifying the location of the CC stretching modes of the Pt-ethylene groups, a topic of considerable disagreement in the literature.  相似文献   

9.
Mixed-ligand complex compounds [Pb(Phen)(i-Bu2PS2)]2 (I) and [Pb(2,2′-Bipy)(i-Bu2PS2)]2 (II) were synthesized. Their structures were determined from X-ray diffraction data (X8 APEX diffractometer, MoK α radiation, 6392 Fhkl , R = 0.0233 for I and 3937 F hkl , R = 0.0252 for II). Crystals I are triclinic: a = 10.2662(3) Å, b = 12.3037(2) Å, c = 14.8444(4) Å; α = 92.054(1)°, β = 103.473(1)°, γ = 105.561(1)°, V = 1746.89(8) Å3, Z = 2, ρcalc = 1.532 g/cm3, space group P . Crystals II are monoclinic: a = 9.3462(3) Å, b = 26.3310(12) Å, c = 28.5345(13) Å; β = 96.436(1)°, V = 6977.9(5) Å3, Z = 8, ρcalc = 1.489 g/cm3, space group P21/n. The structures are built from mononuclear molecules. In both structures, the intermolecular contacts between the Pb and S atoms of the neighboring mononuclear molecules form supramolecular assemblies involving two molecules. The environment of the Pb atoms in the assemblies is a pentagonal bipyramid, N2S4+1. The assemblies are joined into ribbons by π-π interactions of the Phen rings in I and C…C short contacts between the pyridine rings in II. Original Russian Text Copyright ? 2008 by R. F. Klevtsova, E. A. Sankova, T. E. Kokina, L. A. Glinskaya, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 1, pp. 123–131, January–February, 2008.  相似文献   

10.
Single crystal XRD is used to study the crystal structure of a new compound containing the dicarbollyl cluster anion Co(III) with the composition [CuPhen3][Co(C2B9H11)2]2·CH3CN, where Phen is 1,10-phenanthroline. The crystallographic data: C46H71B36N7Co2Cu, M = 1292.66, monoclinic system, P21/c space group, unit cell parameters a = 14.7178(2) ?, b = 19.5640(4) ?, c = 22.8663(5) ?, β = 106.6601(7)°, V = 6307.75(33) ?3, Z = 4, d x = 1.361 g/cm3, T = 100 K, μ = 0.90 mm−1. The structure is solved by the direct method and refined by the full-matrix LSM in an anisotropic-isotropic (for H atoms) approximation up to the final agreement factors R 1 = 0.0370, wR 2 = 0.0869 for 13,807 I hkl ≥ 2 σ I out of 18,295 measured I hkl . The structure consists of [CuPhen3] cations, Co(C2B9H11)2 anions, and acetonitrile molecules MeCN. The central Cu atom in the cation in the general position, and its coordination geometry is a distorted extended octahedron formed by six nitrogen atoms of the three bidentate Phen ligands. The coordination of Cu(II) in the cation is (2+2+2) with two long axial and four shorter equatorial Cu-N bonds, whose average lengths are 2.239(2) ? and 2.077(1) ? respectively. Each anion has its own position of the -C2-groups; for Co(1), it is a quasi-gauche-configuration; for Co(2), a quasi-trans-configuration.  相似文献   

11.
Reaction of tin tetrachloride with the appropriate Grignard reagent gave Sn[C6H4-CH(OCH2)2]4 (2), which was transformed to Sn[C6H4-CHO]4 (3) and its hydrazido and amino derivatives Sn[C6H4-CHN-NH-C6H3-2,4-(NO2)2]4 (5) and Sn{C6H4-CH[N(C2H4)2O]2}4 (8). Oxidation of (3) produced Sn[C6H4-COOH]4 (4) while reduction of (3) gave Sn[C6H4-CH2-OH]4 (6). From the acid 4, an amino acid Sn[C6H4-CO-NH-CH2-CO-OCH3]4 (7) could be obtained by reaction with the methyl ester of glycine. All compounds were isolated in pure form with yields of 40-64% and were characterised by spectroscopic means (heteronuclear NMR) or by X-ray structure determination (3).  相似文献   

12.
Reaction of the neutral tricarbaborane nido-7,8,9-C3B8H12 (1) with triethylamine in CH2Cl2 led to quantitative deprotonation and isolation of the corresponding Et3NH+ salt of the [nido-7,8,9-C3B8H11] anion (2). This was converted into PSH+ and Me4N+ salts via metathetic cation exchange. Heating of the solid Me4N+[7,8,9-C3B8H11] in mineral oil at 350 °C for 2 h resulted in thermal rearrangement and isolation of the cage isomeric compound Me4N+[7,8,10-C3B8H11]. Finally, compound 1 was directly complexed via reaction with [CpFe(CO)2]2 (Cp = η5-C5H5) to generate the ferratricarbollide sandwich [1-Cp-closo-1,2,4,10-FeC3B8H11] (4) in 60% yield. The structures of all the generic compounds of tricarbollide chemistry, 1 (PSH+ salt), 2 (MePPh3+salt), and 4, were established unambiguously by an X-ray diffraction analysis.  相似文献   

13.
Thermal treatment of C9H7SiMe2C9H7 and C9H7Me2SiOSiMe2C9H7 with Ru3(CO)12 in refluxing xylene gave the corresponding diruthenium complexes (E)[(η5-C9H6)Ru(CO)]2(μ-CO)2 [E = Me2Si (1), Me2SiOSiMe2 (2)]. A desilylation product [(η5-C9H7)Ru(CO)]2(μ-CO)2 (3) was also obtained in the latter case. Similar treatment of C9H7Me2SiSiMe2C9H7 with Ru3(CO)12 gave a novel indenyl nonanuclear ruthenium cluster Ru96-C)(CO)143522-C9H7)2 (5) with carbon-centered tricapped trigonal prism geometry, in addition to the diruthenium complex (Me2SiSiMe2)[(η5-C9H6)Ru(CO)]2(μ-CO)2 (4) and the desilylation product 3. Complex 4 can undergo a thermal rearrangement to form the product [(Me2Si)(η5-C9H6)Ru(CO)2]2 (6). The molecular structures of 1, 2, 4, 5, and 6 were determined by X-ray diffraction.  相似文献   

14.
The synthesis and X-ray characterization of ansa-metallocene dichloride titanium and zirconium complexes of the type [Me2Si(η5-C5H2(SiMe3)2)2]MCl2 (M=Zr (1), Ti (2)) are reported. The complexes have been tested for ethylene polymerization.  相似文献   

15.
Protonation of the cycloheptatriene complex [W(CO)36-C7H8)] with H[BF4] · Et2O in CH2Cl2 affords the cycloheptadienyl system [W(CO)35-C7H9)][BF4] (1). Complex 1 reacts with NaI to yield [WI(CO)35-C7H9)], which is a precursor to [W(CO)2(NCMe)33-C7H9)][BF4], albeit in very low yield. The dicarbonyl derivatives [W(CO)2L25-C7H9)]+ (L2=2PPh3, 4, or dppm, 5) were obtained, respectively, by H[BF4] · Et2O protonation of [W(CO)2(PPh3)(η6-C7H8)] in the presence of PPh3 and reaction of 1 with dppm. The X-ray crystal structure of 4 (as a 1/2 CH2Cl2 solvate) reveals that the two PPh3 ligands are mutually trans and are located beneath the central dienyl carbon and the centre of the edge bridge. The first examples of cyclooctadienyl tungsten complexes [WBr(CO)2(NCMe)2(1-3-η:5,6-C8H11)] (6) and [WBr(CO)2(NCMe)2(1-3-η:4,5-C8H11)] (7) were synthesised by reaction of [W(CO)3(NCR)3] (R=Me or Prn) with 3-Br-1,5-cod/6-Br-1,4-cod or 5-Br-1,3-cod/3-Br-1,4-cod (cod=cyclooctadiene), respectively. Complexes 6 and 7 are precursors to the pentahapto-bonded cyclooctadienyl tungsten species [W(CO)2(dppm)(1-3:5,6-η-C8H11)][BF4] and [W(CO)2(dppe)(1-5-η-C8H11)][BF4] · CH2Cl2.  相似文献   

16.
(C8H11N)2·Zn(OAc)2 (1a), (C8H11N)2·Cu(OAc)2 (1b), and (C8H11N)2·CuCl2 complexes are synthesized by a simple one-pot method. The crystal structures of 1a, 1b, and 1c are determined by X-ray crystallography. The complexes are also characterized by NMR, IR, MS, and elemental analysis and used as the catalysts applied to the Henry reaction; moderate to high yields are obtained at room temperature.  相似文献   

17.
The reaction of indium thiocyanate with bipyridine (4,4-Bipy) and urotropine (Ur) gave [H2(4,4′-Bipy)][In(H2O)2(NCS)4]2 (I) and [HUr]2[In(H2O)(NCS)5] · 2H2O (II), which were identified using elemental analysis, IR spectra, and thermogravimetric analysis. The thermal decomposition of compound I and II ends at 650 and 640°C, respectively, and gives In2O3. X-Ray diffraction analysis of compound I showed that complex anions in the crystal form chains through O-H…S hydrogen bonds. The anion chains form a close packing of columns with bipyridine cations located in the voids. Original Russian Text ? S.P. Petrosyants, A.B. Ilyukhin, V.A. Ketsko, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 6, pp. 951–955.  相似文献   

18.
Two new dicyanamide coordination polymers, {Mn(dmpz)[N(CN)2]2}2 (1) and {Cu(dmpz)[N(CN)2]2}2 (2)(dmpz=3,5-dimethylpyrazole), were synthesized and characterized by single crystal X-ray diffraction analysis and IR spectroscopy. In 1 and 2 the metal ions have two different coordination modes, where one is coordinated to four dicyanamide anions and two monodentate dmpz molecules to form a slightly distorted octahedral geometry, while the other adopts octahedral geometry, surrounded by four nitrile N atoms and two amide N atoms of the dicyanamide anions. Both complexes contain two alternating chains that are parallel to each other.  相似文献   

19.
X-ray diffraction data have been used to determine crystal structures of coordination compounds [CoPhen{ (i-C4H9)2PS2}2] (I) and [Co(2,2′-Bipy){ (i-C4H9)2PS2}2] (II) (X8-APEX diffractometer, MoK α∔ -radiation, 3083 F hkl , R = 0.0647 for I and 5381 F hkl , R = 0.0597 for II). I is triclinic, a = 11.244(1) Å, b = 14.892(2) Å, c = 21.419(4) Å, α = 71.867(4)°, β = 81.553(4)°, γ = 76.777(4)°, V = 3306,9(8) Å3; Z = 4, ρcalc = 1.321 g/cm3, space group ; II is monoclinic, a = 14.693(2) Å; b = 20.868(3) Å, c = 11.417(1) Å; β = 106.46(5)°; V = 3357.1(7) Å3, Z = 4, ρcalc = 1.254 g/cm3, space group P21/c. The structures are built from discrete mononuclear molecules. Coordination polyhedra of Co atoms are distorted octahedra formed by four S atoms of two bi-dentate chelating ligands (i-C4H9)2PS 2 and two N atoms of two bi-dentate chelating Phen or 2,2′-Bipy molecules. The interaction of the molecules in the structures of I and II has been analyzed. It has been found that the molecules of I and II form dimer ensembles owing to π-π-interactions of Phen or 2,2′-Bipy. Original Russian Text Copyright ? 2005 by R. F. Klevtzova, L. A. Glinskaya, T. E. Kokina, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 4, pp.705–714, July–August, 2005.  相似文献   

20.
The reaction of the labile compound [Re2(CO)8(CH3CN)2] with trans-1,2-bis(2-pyridyl)ethene (C12H10N2) at room temperature in tetrahydrofuran affords the compounds [Re2(μ:η3-C12H10N2)(CO)8] (1) and the oxidative addition product [Re2(μ-H)(μ:η3-C12H9N2)(CO)7] (2). When the reaction is carried out at temperatures of refluxing tetrahydrofuran, besides compounds 1 and 2, the oxidative addition product [Re2(μ-H)(μ:η4-C12H9N2)(CO)6] (3), the insertion product [Re2(μ:η4-C12H10N2)(CO)8] (4) and [Re2(μ:η6-C24H18N4)(CO)6] (5) are obtained. Compound 5 contains the organic ligand rtct-tetrakis(2-pyridyl)cyclobutandiyl which is derived from a [2 + 2] cycloaddition of 1,2-bis(2-pyridyl)ethene mediated by its coordination to the bimetallic framework. The molecular structures of 1, 2, 4 and 5 were confirmed by X-ray crystallographic studies.  相似文献   

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