共查询到20条相似文献,搜索用时 31 毫秒
1.
E. Vajda T. Székely I. Hargittai A.K. Maltsev E.G. Baskir O.M. Nefedov J. Brunvoll 《Journal of organometallic chemistry》1980,188(3):321-327
An electron diffraction analysis of the molecular structure of the title compound has been carried out, and related vibrational spectroscopic measurements and calculations have been made. The main bond lengths (rg and bond angles rα) are as follows: SiCl, 202.8(2); SiC, 185.1(10); CCl, 179.4(11); CH, 111.2(18) pm; SiCCl, 111.7(4);l ClSiC, 109.95(21)°. The conformation of the molecule is staggered. The barrier to internal rotation is estimated to be around 10 kJ mol?1. 相似文献
2.
H. D. Hausen K. Sille J. Weidlein W. Schwarz 《Journal of organometallic chemistry》1978,160(2):411-419
Trimethylgallium reacts with acetic acid in a molar ratio yielding methylgallium diacetate, CH3Ga(OOCCH3)2? The structure is determined by vibrational spectroscopy and the crystal structure is described. Methylgallium diacetate crystallizes in the monoclinic space group P21/c with lattice constants a 776.5, b 1428.9, c 1406.3 pm, β 91.87° and eight formula units per cell. The monomers are linked together by acetate groups forming polymeric, waved layers. Besides the bridging acetate there are also “free” acetate groups coordinated at the distorted trigonal-bipyramidal coordinated Ga(1) atom. A second gallium atom Ga(2) is coordinated distorted tetrahedrally, the acetate groups bonded to Ga(2) being all bridging. The mean intermolecular distances are: GaC 194.6 pm, Ga(1)Oapical 215.3 pm, Ga(1)Oeq(bridge) 194.3 pm, Ga(1)Oeq(free) 187.3 pm, Ga(2)O 191.3 pm, CC 151.5 pm, CO 119.4 pm, CO 131.1 pm, CO 127.3 pm. 相似文献
3.
The structure of Mn(NO)3PPh3 has been analyzed by single-crystal X-ray diffraction. It shows a tetrahedral geometry with essentially linear nitrosyl groups, and an eclipsed configuration around the MnP bond. Average distances and angles are: MnN 1.686(7) Å, MnP 2.315(2) Å, NO 1.165(10) Å, PC 1.815(4) Å, MnNO 177.2(7)°, PMnN 103.6(2)°, NMnN 114.7(4)°. Final R factor 7.3% for 2064 non-zero reflections. The structure of the five-coordinate nitrito complex Mn(NO)2(ONO)(PEt3)2 is also mentioned briefly. 相似文献
4.
The crystal and molecular structure of hexaphenylditin selenide (C6H5)3SnSeSn(G6H5)3 was determined by X-ray diffraction data and was refined to R 0.055. The compound is monoclinic, space group P21, with a 9.950(4), b 18.650(7), c 18.066(6) Å, β 106.81(4)°, Z 4. The two molecules in the asymmetric unit differ slightly in their conformations, both having approximate C2 symmetry. Bond lengths and angles are: SnSe 2.526 (2.521(3) ? 2.538(3)) Å; SnC 2.138 (2.107(16)?2.168(19)) Å; SnSeSn 103.4(1)°, 105.2(1)°. There are only slight angular distortions at the SnSeC3 tetrahedra (SeSnC angles: 104.3(5)?114.8(4)°). The bond data indicate essentially single bonds around the Sn atoms. 相似文献
5.
Rudolf Allmann Wolfgang Henke Peter Krommes Jörg Lorberth 《Journal of organometallic chemistry》1978,162(3):283-287
The molecular and crystal structure of tris(bistrimethylsilylamin)thallium was determined by means of single-crystal X-ray spectroscopy: in the space group P1c with a = 16.447(7), c = 8.456(7) Å; and Dc = 1.149 g cm?3 two molecules are located in the unit cell. The compound is isomorphous to the analogues Fe[N(SiMe3)2]3 or Al[N(SiMe3)2]3, respectively, which show a propellar-twist of the Si2N-groups versus the plane of the metal atom and the three nitrogen-atoms: Tl(N)3/Si2N 49.1°; SiNSi 122.6°; NSiC 111.8°; CSiC 107.1°; TlN 2.089 Å;; SiN 1.738 Å;; 1.889 Å;. 相似文献
6.
Dimethylamine reacts with Ru3(CO)12 to produce the η2-hydrido-η-formamido cluster complex HRu(OCN(CH3)2)(CO)10 (I). This formulation is consistent with spectroscopic features such as the absence of v(NH) in the infrared, the presence in the Raman of v(RuHRu) at 1400 cm?1 (v(RuDRu) at 990 cm?1) and indication in the 1H NMR of diastereotopic methyl groups bonded to the nitrogen atom. Since these data could not lead to an unequivocal structure assignment a single crystal X-ray study at 115 K was undertaken. The complex crystallizes in the triclinic space group, P with cell dimensions; a 7.299(33) », b 9.5037(40) », c 13.7454(57) », α 91.876(34)°, β 96.387(34)°, γ 95.341(34)° and Z = 2. The structure was solved by a combination of Patterson and Fourier techniques and refined by full matrix least squares to a final R = 0.054 and Rω = 0.074 for 3074 unique reflections. The three ruthenium atoms define a triangle of unequal sides with both the hydride and formamido groups bridging the longest edge; the formamido group is coordinated through the carbon and oxygen atoms. The edge of the ruthenium triangle bridged both by the hydrogen atom and the formamido group is 2.8755(15) »; the other two edges of the ruthenium triangle are observed to be 2.8319(15) and 2.8577(14) », respectively. In the formamido group the distance CO 1.287(9) » and CN 1.340(10) » reflect partial double bond charater in each bond consistent with observation of two chemically distinct methyl groups on the dinitrogen atom. The hydrogen atom bridging one edge of the ruthenium triangle is asymmetrically positioned at 1.73(9) » from the ruthenium atom bonded to the oxygen atom and 1.91(9) » from the ruthenium atom bonded to the carbon atom of the carboxamido group. 相似文献
7.
en Two differnt crystal modifications of hexaphenyldigermanium sulfide (C6H5GeSGe(C6H5)3 (I and II were obtained by crystallization from hot benzene/methanol or form ethanol at 20°C. Single crystal X-ray structural analyses for both I (low temperature data at ?130°C) and II (at 20°C) (I, R = 0.046; II, R = 0.048) were performed. I is monoclinic, P21/c, with a = 11.020(3), b = 15.473(3), c 18.606(3) »,π = 106.92(2)°, Z = 4; II is orthorhombic, P212121, with a = 2.617(2), b = 17.345(3), c = 18.408(3) », Z = 4.The molecules have different conformeric structures with respect to a rotation of the (C6H6)3Ge groups around the Ge bonds with very similar bond lenghts and angles. Bond data for I(II) are: GeS 2.212(1) and 2.261(1) » (2.227(2) and 2.240(2) »); GeC 1.933(4) ? 1.971(4), mean 1.945(5) » (1.931(7)?1.954(7), mean 1.943(4) »); GeSGe 111.2(1)° (110.7(1)°). The Ge bond lenghts are comparable to those in thiogermanates and do not indicate significant π-bond contributions. 相似文献
8.
C. Anklin P.S. Pregosin F. Bachechi P. Mura L. Zambonelli 《Journal of organometallic chemistry》1981,222(1):175-185
Platinum(II) and palladium(II) complexes containing chelating acyl ligands have been synthesized from salicylaldehyde, 2-hydroxynaphthaldehyde and 2-hydroxy-3-methoxybenzaldehyde. The platinum(II) complexes [Pt(acyl)L2], acyl OC6H4CO, OC10H6CO, O(m-CH3OC6H3CO), L tertiary phosphine, 1/2 diphenylphosphinoethane, can be isolated with both monodentate and chelating diphosphines, whereas for palladium only the compounds with chelating phosphines are readily obtainable. The reactions of [Pt(OC6H4CO)L2] with HCl afford trans-[PtCl(OHC6H4CO)L2], L monodentate tertiary phosphine and cis-[PtCl(OHC6H4CO)L2], L2 1,2-bis-diphenylphosphinoethane, in which the metal—carbon bond remains intact. The structure of [Pt(OC6H4CO)-(P(p-CH3C6H4)3)2] has been determined by X-ray diffraction methods and found to have the expected square planar structure. Some relevant bond lengths and angles are: PtP; 2.271(4) and 2.348(5) Å; PtC; 1.96(2) Å and PtO; 2.07(1) Å; PPtP 101°, CPtO 82°. 相似文献
9.
Diphenylcyclopropenethione reacts with Fe2(CO)9 in THF to give tetracarbonyl(diphenylcyclopropenethione)iron (C3Ph2S)Fe(CO)4. The crystal structure was determined by single crystal X-ray analysis. The compound crystallizes in the triclinic space group P with lattice constants a 1520.3(5), b 1026.1(3), c 933.5(2) pm; α 120.58(2), β 109.36(2), γ 111.72(2)°; Z 2. The molecule consists of an unchanged diphenylcyclopropenethione ligand coordinated via the sulphur atom to an Fe(CO)4 group in the axial position. The CS distance is 165.2(7) pm with an FeSC angle of 111.2(2)°. 相似文献
10.
G.R. Clark T.J. Collins K. Marsden W.R. Roper 《Journal of organometallic chemistry》1983,259(2):215-232
Reaction of HgR2 with OsHCl(CS)(PPh3)3 yields red, five-coordinate, OsRCl-(CS)(PPh3)2 (R = p-tolyl). From this have been derived the compounds OsRX(CS)(PPh3)2 with X = Br, I, S2CNEt2, O2CMe, O2CCF3. These compounds add an additional ligand, MeCN, CO or CNR to form colourless, six coordinate arylthiocarbonyl complexes, which undergo migratory-insertion reactions to form red, dihapto-thioacyl complexes. The crystal structure of a representative example, Os(η2-CSR)(η1-O2CCF3)(CO)PPh3)2 has been determined. The red equant crystals are orthorhombic, space group P212121, a 11.584(1), b 19.184(2), c 18.90(1) Å, V 4199 Å3, Z 4. The structure was solved by conventional heavy-atom methods and refined by full-matrix least-squares employing anisotropic thermal parameters for all non-hydrogen atoms except the carbon atoms of the triphenylphosphines. The final R factor is 0.057 for 2868 observed reflections.The coordination geometry in the monomeric complex is that of an octahedron distorted by the constraints of the ligands. The triphenyl phosphine ligands are mutually trans; the equatorial plane contains carbonyl, monohapto-trifluoroacetate, and dihapto-thioacyl ligands. Bond distances and angles are OsP 2.405, 2.407(4) Å; POsP 173.9(1)°; OsCO 1.83(2) Å; Os-O (trifluoroacetate) 2.206(11) Å; OsC (thioacyl) 1.91(2); OsS 2.513(6); CS 1.72 Å. The CS bond length implies a reduction in bond order from 2.0 to approx. 1.5 upon coordination to the metal.The η2-thioacyl ligand in Os(η2-CSR)Cl(CNR)(PPh3)2 is methylated with methyl triflate and further reaction with LiCl produces the thiocarbene complex OsCl2(C[SMe]R)(CNR)(PPh3)2. 相似文献
11.
The enthalpy of the reaction: Pt(PPh3)2 (CH2CH2)(cryst.) + C(CN)2C(CN)2 (g) → Pt(PPh3)2 {C(CN)2C(CN)2}(cryst.) + CH2 CH2 (g) has been determined as ΔH298=?155.8±8.0 kJ·mol?1, from solution calorimetry. The interpretation, that the platinumethylene bond is much weaker than the platinumtetracyanoethylene bond, is contrary to conclusions drawn recently from electron emission spectroscopic studies, but in agreement with available structural data. 相似文献
12.
Arne Haaland Svein Samdal Oddvar Stokkeland Johann Weidlein 《Journal of organometallic chemistry》1977,134(2):165-171
The molecular structure of (CH3)3AlO(CH3)2 has been determined by gas phase electron diffraction. The main molecular parameters are AlC = 1.973(11), AlO = 2.014(14), OC = 1.436(3) Å, OAlC = 98.7(1.5), AlOC = 122.6 (0.5) and COC = 114.5(1.7)°. The OC bond distance and the COC valence angle are significantly larger than those in free dimethyl ether. The three valencies of the oxygen atom appear to lie in one plane. It is suggested that the planarity of the oxygen atom is due to across-angle repulsion Al?C(O). 相似文献
13.
Reaction of phenylimido tungsten tetrachloride with MeOH and t-butylamine gave the dimeric complexes [W(NPh)(μ-OMe)(OMe)3]2 and [W(NPh)(μ-OMe)(OMe)2Cl]2. With ethanol [W(NPh)(μ-OEt)(OEt)2Cl]2 was formed whereas isopropyl and neopentyl alcohols gave the monomeric complexes [W(NPh)(OR)4(NH2CMe3)](R = CHMe2, CH2CMe3); t-butanol gave [W(NPh)(OCMe3)3Cl(NH2CMe3)] which could not be converted to [W(NPh) (OCMe3)4]. Further reaction of [W(NPh)(μ-OMe)(OMe)3]2 with o-HOC6H4CH = NC6H3Me2(salim-H) gave the salicylaldimine complex [W(NPh)(OMC)3(salim)]. The products were characterised by analytical data, IR, 1H NMR, 13C NMR and mass spectroscopy. The crystal and molecular structures of the title complexes have been determined from single crystal X-ray diffractometer data. Crystals of [W(NPh)(μ-OMe)(OMe)3]2are triclinic with a = 8.473(7), b = 10.776(5), c = 7.683(Å, α = 102.26(3), β = 102.68(4), γ = 71.13(6)°, space group P Crystals of 3) [W(NPh)(OCMe3)3Cl(NH2CMe3) are monoclinic with a = 9.341(2), b = 29.608(7), c = 10.257(2) Å, β = 106.28(2)°, space group, P21/c. Both structures were solved by Patterson and Fourier methods and refined to R = 0.075 for the 1022 observed data of [W(NPh) (μ-OMe)(OMe)3]2 and to R = 0.074. For the 2033 observed data of [W(NPh)(OCMe3)3Cl(NH2CMe3). The former molecule is shown to be a dimer, the two halves of the molecule being related by a centre of symmetry. Both W atoms adopt a distorted octahedral coordination geometry and they are linked by two methoxy bridges. Trans to one of the bridging donors is the phenyl imido group with a WN bond length of 1.61(4) Å; the remaining coordination sites are filled with methoxy groups. The structure of W(NPh)(OCMe3)3 Cl(NH2CMe3) is monomeric with the phenylimido group trans to the NH2CMe3 ligand in a distorted octahedral coordination geometry. Remaining sites are filled with the chloride and 3 OCMe3 ligands. The WN (imido) bond length is 1.71(2) Å, whilst WN(amine) is 2.40(2) Å 相似文献
14.
The title compound has been prepared by reaction of (C5H5)2Cr with oxindole (indole with CO in place of CH2 at the 2-position). Red single crystals belong to space group P21/c with a = 10.107(4) Å, b = 22.496(7) Å, c = 9.210(3) Å, β = 93.26(3)°, V = 2091(2), and Z = 2. The centrosymmetric molecule has a CrCr distance of 2.495(4) Å. The mean CrO and CrN distances for the bonds to bridging oxindolate anions are 2.024(7) and 2.065(8) Å, respectively. There is an oxindole molecule bound at each end with a CrO axial bond of length 2.341(8) Å and a hydrogen bond from the oxindole NH group to an equatorial oxygen atom of length 2.83(1) Å. The significance of this compound with respect to CrCr bonding is discussed. 相似文献
15.
Two silyl-zirconium compounds (η-C5H5)2ZrCl[Si(CH3)3] (I) and (η-C5H5)2-Zr[Si(CH3)3]2 (II), have been prepared by the reaction of (η-C5H5)2ZrCl2 with Hg[Si(CH3)3]2 in refluxing benzene. While I is unreactive toward 1-hexyne (55–60°C) and CO (350 psi), the zirconiumsilicon bond is cleaved by electrophiles such as Cl2, HgCl2, and AlCl3. 相似文献
16.
G. Fritz St. Lauble R. Befurt K. P. Peters E.-M. Peters F. H. G. von Schnering 《无机化学与普通化学杂志》1993,619(9):1494-1511
Formation of Organosilicon Compounds. 110. Reactions of (Cl3Si)2CCl2 and its Si-methylated Derivatives as well as of (Cl3Si)2CHCl, (Cl3Si)2C(Cl)Me and Me2CCl2 with Silicon (Cu cat.) The reactions of (Cl3Si)2CCl2 1 , its Si-methylated derivatives (Me3Si)2CCl2 8 , Me3Si? CCl2? SiMe2Cl 9 , (ClMe2Si)2CCl2 10 , Me3Si? CCl2? SiMeCl2 11 , Cl2MeSi? CCl2? SiCl3 12 as well as of (Cl3Si)2CHCl 38 , (Cl3Si)2CClMe 39 and of Me2CCl2 with Si (Cu cat.) in a fluid bed reactor ( 38 and 39 also in a stirred solid bedreactor) arc presented. While (Cl3Si)2CCl2 1 yields C(SiCl3)4 2 the 1,1,3,3-tetrachloro-2,2,4,4-tetrakis(trichlorsilyl)-1,3-disilacyclobutane Si6C2Cl16 3 and the related C-spiro linked disilacyclobutanes Si8C3Cl20 4 , Si10C4Cl24 5 , Si12C5Cl28 6 , Si14C6Cl32 7 this type of compounds is not obtained starting from the Si-methylated derivatives 8, 9, 10, 11 They Produce a number of variously Si-chlorinated and -methylated tetrasila- and trisilamethanes. However, Cl2MeSi? CCl2? SiCl3 12 forms besides of Si-chlorinated trisilamethanes also the disilacyclobutanes Si6C2Cl15Me 34 and cis- and trans Si6C2Cl14Me2 35 as well as the spiro-linked disilacyclobutanes Si8C3Cl19Me 36 , Si8C3Cl18Me2 37 . (Cl3Si)2CHCl 38 mainly yields HC(SiCl3)3 31 and also the disilacyclobutanes cis- and trans-(Cl3Si)HC(SiCl2)2CH(SiCl3) 41 and (Cl3Si)2C(SiCl2)2CH(SiCl3) 45 the 1,3,5-trisilacyclohexane [Cl3Si(H)C? SiCl2]3 44 as well as [(Cl3Si)2CH]2SiCl2, and (Cl3Si)2CClMe 39 mainly yields (Cl3Si)2C?CH2and (Cl3Si)2besides of HC(SiCl3)3, MeC(SiCl3)3and (Cl3Si)3C? SiCl2Me.,. Me2CCl2 59 mainly yields Me(Cl)C?CH2, Me2CHCl and HCl2Si? CMe2? SiCl3, besides of Me2C(SiCl3)2 and Me2C(SiCl2H)2 Compound 3 crystallizes triclinically in the space group P1 (Nr. 2) mit a = 900,3, b = 914,0, c = 855,3 pm, α = 116,45°, β = 101,44°, γ = 95,86° and one molecule per unit cell. Compound 4 crystallizes monoclinically in thc space group C2/c (no. 15) with a = 3158.3,b = I 103.7, c = 2037.4 pm, β = 1 16.62° and 8 molecules pcr unit cell. The disilacyclobutane ring of compound 3 is plane, showing a mean distance of d (Si-C) =19 1.8 pm and the usual deformations of endocyclic angles: αSi = 94,2°> 85,8° = αC.The spiro-linked disilacyclobutane rings of compound 4 are slightly folded by a mean angle of (19.0°). Their mean distances were found to be d (Si? C) = 190.4 pm relating to the central carbon atom and 192.0 pm to the outer ones, respectively. The deformations of endocyclic angles: αSi = 93,9°> 84,4° = αC are comparable to those of compound 3. 相似文献
17.
Dimethylaluminium- and dimethylgallium-N,N′-dimethylacetamidine (I and II) are doubly associated forming a puckered eight-membered ring. They crystallize isostructurally in the monoclinic space group P21/c with two dimers per unit cell. The lattice constants of I are a 8.187, b 7.266, c 14.778 Å, β 103.58° and those of II a 8.163, b 7.277, c 14.835 Å, β 103.46°. The MN and the NC bond lengths within the rings are nearly equal, their mean values are for I: AlN 1.925 Å, CN 1.330 Å and for II: GaN 1.979 Å, CN 1.335 Å. This is also true for the exocyclic bond lengths with average values AlC 1.975 Å, NC 1.474 Å, CC 1.509 Å (for I) and GaC 1.998 Å, NC 1.484 Å and CC 1.507 Å (for II). The metal atoms are tetrahedrally coordinated, and the distortion is only slight. The final R-values are 0.034 and 0.056, respectively. 相似文献
18.
Paul Bleckmann Hartwig Maly Rolf Minkwitz Wilhelm P. Neumann Bärbel Watta Gottfried Olbrich 《Tetrahedron letters》1982,23(45):4655-4658
Free stannylenes Me2Sn and (CD3)2Sn, generated thermally from the cyclic hexamers or by microwave discharge from Me2SnH2, are isolated by Argon matrix technique. All IR bands could be attributed to the important molecular vibrations by normal coordinate analysis. As shown by ab initio SCF calculations, Me2Sn has a singlet groud state, the angle CSnC is 95.3°, the CSn bond length is 2.203 Å. 相似文献
19.
Michael I. Bruce Trevor W. Hambley MichaeL R. Snow A.Geoffrey Swincer 《Journal of organometallic chemistry》1982,235(1):105-112
The title complex was obtained from the adduct of C2(CN)4 and Rh(CCPh)-(CO)(PPh3)2 by simple substitution of CO in refluxing acetonitrile. Crystals of the complex are orthorhombic, with a 10.058(2), b 20.008(4), c 21.594(5) Å, space group P212121, Z 4. The rhodium has approximate trigonal bipyramidal coordination, with apical NCMe and C2Ph ligands: RhC2Ph, 1.939(18); RhC(olefinic), 2.151, 2.157(19); RhN, 2.051(16); RhP, 2.377, 2.397(6) Å. 相似文献
20.
The thermal decomposition of the complexes trans-[Pt(X)(CH3)L2] (L P(C2H5)3; X Cl, Br, I, CN) in decalin at 170 and 200°C affords methane platinum metal and [Pt(X)2L2]. The kinetics of the decomposition of the complexes were determined by monitoring the appearance of methane by GLC. The observed first-order rate constant was found to be independent on the nature of the ligand X. The thermal decomposition of the trideuteriomethyl complexes [Pt(X)(CD3)L2] (X I, CN) in decalin-d18 at 170 and 200°C was studied by GLC/MS. The thermolysis affords CD3H and CD4 in ratios which are independent of the nature of X and of the temperature used. The mass spectra of the complexes were also examined. A relative scale of platinum-to-methyl bond dissociation energies has been established by measuring the appearance potential of the fragment ion [Pt(X)L2]+ and the ionization energies in the series [Pt(X)(CH3)L2]. Ionization potentials and PtCH3 bond energies show a clear dependence on the nature of X which is not reflected in corresponding changes in the decomposition rates. 相似文献