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1.
Michael I. Bruce Brian K. Nicholson Jennifer M. Patrick Allan H. White 《Journal of organometallic chemistry》1983,254(3):361-369
The X-ray structure of H4Ru4(CO)9(PMe2Ph)[P(OC6H4Me-p)3][P(OCH2)3CEt], a chiral cluster complex, has been determined. The complex is triclinic, space group P, a 19.812(7), b 14.299(4), c 10.323(4) Å, α 100.09(3), β 98.18(3), γ 102.23(3)°. The unit cell contains an enantiomeric pair of molecules. The Ru4 core contains two short (av. 2.785 Å) and four long (2.967 Å) RuRu separations with approximate D2d symmetry. RuP separations are 2.254(6) Å [to P(OCH2)3CEt], 2.270(6) Å [to P(OC6H4Me-p)3] and 2.326(7) Å [to PMe2Ph]; all P-donor ligands are trans to short RuRu vectors. 相似文献
2.
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
3.
The structure of (Ph3SiN)2C has been determined by single crystal X-ray diffraction. The structure was solved by direct methods and refined to R = 0.071 for 593 independent diffractometer data. The crystals are rhombohedral, R with a = b = c 18.201(20) Å, α = β = γ = 48.82(2)°, and Z = 4. The three crystallographically independent molecules each have linear SiNCNSi chains lying along the crystallographic threefold axes; in two of the molecules the central carbon atom lies on a centre of symmetry. Principal mean bond lengths and angles are: Si, 1.696(25); SiC, 1.846(20); NC, 1.164(30); CC, 1.387(14) Å; CSi, 108.2(6); and CSiC, 110.8(6)°. 相似文献
4.
The crystal structure of Ph3SnNCS has been determined by single crystal X-ray diffraction. The crystals are monoclinic, P21, a = 19.02(3), b = 11.67(2), c = 15.49(2)Å;, β = 95.64(10)°, Z = 8. The molecules are arranged in infinite zig-zag S…SnNCS…Sn&.sbnd; chains similar to those in Me3SnNCS, but with slightly longer SnN, shorter SnS bonds, and almost planar SnC3 units. Principal mean bond lengths and angles are: SnN, 2.22(5); NC, 1.17(8); CS, 1.58(7); SSn, 2.92(1); SnC, 2.09(3); CC, 1.38(2)Å; SnNCm 161(4); CSSn, 97(3); SSnN, 175(3) and CSnC, 119.8(1.5)°. 相似文献
5.
R.B. King 《Journal of organometallic chemistry》1975,100(1):111-125
The molecular structure of [(C6H5)3P]2Pt(C5H8) has been determined from three-dimensional X-ray diffraction data (R = 0.045 for 6033 reflections). The crystal belongs to the triclinic system, space group P, with two formula units in a cell of dimensions: a = 18.557(2), b = 10.216(2), c = 9.647(2) Å, α = 98.29 (3), β = 73.44(2), and γ = 88.34(2)°.One of the olefinic bonds of dimethylallene, which has no adjacent methyl groups, is coordinated to the platinum atom: PtC(1) = 2.108(8), PtC(2) = 2.049(7) Å. The coordinated dimethylallene molecule is no longer linear, the C(1)C(2)C(3) angle being 140.8(8)°, which is significantly smaller than that found in [(C6H5)3P]2Pd(C3H4). The C(1)C(2) distance is 1.430(11) Å, whereas the uncoordinated bond distance is normal [C(2)C(3) = 1.316(11)Å]. 相似文献
6.
Gerhard Thiele Günther Liehr Ekkehard Lindner 《Journal of organometallic chemistry》1974,70(3):427-435
The molecular structure of [(C6H5)3P]2Pd(C3H4) has been determined from three-dimensional X-ray diffraction data. The crystal belongs to the triclinic system, space group P, with two formula units in a cell of dimensions: a = 19.475(2), b = 10.204(2), c = 18.341(2) Å, α = 108.46(2), β = 85.46(1), and γ = 118.80(1)°.One of the olefinic bonds of allene is coordinated to the palladium atom: PdC(1) = 2.118(9) and PdC(2) = 2.067(8) Å. The coordinated allene is no longer linear, the C(1)C(2)C(3) angle being 148.3(8)°. The C(1)C(2) distance is 1.401(11) Å, whereas the uncoordinated bond remains unchanged [C(2)C(3) = 1.304(12) Å]. The Pd, P(1), P(2), C(1) and C(2) atoms lie almost in the same plane. 相似文献
7.
Colin Eaborn Peter B. Hitchcock Paul D. Lickiss 《Journal of organometallic chemistry》1981,221(1):13-17
The structure of the crowded molecule (Me3Si)3C(SiMe2Ph) has been determined by single crystal X-ray diffraction. The steric strain manifest itself mainly in lengthening of the Me3SiC and Me2PhSiC bonds (average length 1.920(6) ) and closing up of the CSiC angles within the Me3Si and Me2PhSi groups (average 105.2(10)°), with correspondingly large C(1)SiC angles (113.5(13)°; C(1) is the central carbon atom). 相似文献
8.
Michael Laing Magriet J. Nolte Eric Singleton Erwin van der Stok 《Journal of organometallic chemistry》1978,146(1):77-86
The crystal structure of [(C8H12)6H3Me)(OC6H4Me)2} {P(OCH2)3CMe}] has been determined. a 18.32, b 18.98, c 9.35 Å, U 3251 Å3, Pn21a, Z = 4, R = 0.048, 2541 observed data.The coordination about the iridium atom is distorted trigonal bipyramidal; the two phosphorus atoms are equatorial, the σ-bonded carbon is axial, and the bidentate cyclooctadiene is bonded axialequatorial. The IrC(axial) bonds are longer than the IrC(equatorial) bonds: 2.22, 2.26; 2.17, 2.19 Å. The IrC(σ) bond length is 2.19 Å, not significantly different from the formally π-bonded C to Ir distances. The IrP lengths of 2.201 and 2.240 Å and the PIrP angle of 108.7° are normal. The longer IrP bond is in the five-membered chelate ring. The inertness to substitution is discussed. 相似文献
9.
Aristides Christofides Judith A.K. Howard John L. Spencer F.Gordon A. Stone 《Journal of organometallic chemistry》1982,232(3):279-292
Bis(cycloocta-1,5-diene)platinum reacts with 2,3,4,5-tetraphenylfulvene to afford the complex [Pt(η2-CH2C5Ph4)(cod)] (cod C8H12) in which the metal atom is coordinated to the exo-cyclic double bond of the fulvene. Related compounds [Pt(η2-CH2C5Ph4L2] (L PPh3, PMePh2, PMe2Ph, AsPh3 or CNBut have also been prepared and characterised. Reaction of the complexes [Pt(C2H4)2(L)] (L P(cyclo-C6H11)3, PPh3 or AsPh3) with 2,3,4,5-tetraphenylfulvene yields the compounds [Pt(C2H4)(η2-CH2C5PH4)(L)]. NMR data for the new species are reported and discussed. 6,6-Diphenylfulvene reacts with [Pt(cod)2] and PPh3 ( mol ratio) to give the complex [Pt(η2-C5H4CPh2)-(PPh3)2] in which the metal atom is bonded to carbon atoms C(2) and C(3) of the fulvene ring. This was established by an X-ray diffraction study. Crystals are monoclinic, space group P21/n, with Z 4 in a unit cell of dimensions a 13.761(4), b 21.653(13), c 17.395(6) Å, β, 104.46(2)°. The structure has been solved and refined to R 0.064 (R′ 0.064) for 3139 independent diffracted intensifies measured at room temperature. The platinum atom is in a trigonal environment formed by the two ligated phosphorus atoms and the CC bond of the fulvene which is elongated to 1.52(3) Å. The c5 fulvene ring is planar, and makes an angle of 108° with the coordination plane around the platinum. In this plane the metal atom is slightly asymmetrically bonded with PtC 2.15(2) and 2.24(2) Å, and PtP 2.280(6) and 2.301(6) Å. 相似文献
10.
Michael I. Bruce Trevor W. Hambley Michael R. Snow A.Geoffrey Swincer 《Journal of organometallic chemistry》1984,273(3):361-376
Reactions between MX(PPh3)2(η-C5H5) (M = Ru, X = Cl; M = Os, X = Br) and 2-CH2CHC6H4PPh2 afford Ph2)(η-C5H5); the Os complex is obtained in two isomeric forms. The X-ray structure of the major isomer shows the CC double bond (OsC, 2.214, 2.195 Å; CC, 1.57 Å) is almost coplanar with the OsBr vector, with the terminal C cis to Br; the minor isomer is assumed to have the alternative, more sterically congested conformation, with the β-C cis to Br. The chlororuthenium complex reacts with NaOMe/MeOH to give the corresponding hydrido complex, which also exists as two isomers in solution; reaction of this complex with CS2 gives the expected dithio acid derivative Ph2)(η-C5H5), together with small amounts of a complex assumed to be Ph2](η-C5H5). The X-ray structure of the major product reveals an unusual η3-S2C mode of coordination of the dithio acid fragment (RuS, 2.418, 2.426(1) Å; RuC 2.175(4) Å). Crystals of OsBr(η2-CH2CHC6H4P)Ph2)( η-C5H5) are monoclinic, space group P21/n, with a 12.696(2), b 21.719(6), c 15.929(3) Å, β 79.77(2)°, Z = 8; 2867 data (I > 2.5σ(I)) were refined to R = 0.040, Rw = 0.044. Crystals of Ph2)(η-C5H5) are orthorhombic, space group Pbca, with a 8.921(2), b 15.982(9), c 32.216(5) Å, Z = 8; 1685 data (I > 2.5σ(I)) were refined to R = 0.027, Rw = 0.030. 相似文献
11.
A full X-ray structure analysis of two polymorphic modifications of tris(p-chlorophenyl)arsinoxide, C18H12AsOCl3, has been performed. Modification I is triclinic, space group P, Z = 4; modification II is hexagonal, space group P63, Z = 2. The geometrical parameters of the molecules in the two polymorphs are similar; the mean values for the bond distances and angles are: AsO 1.641, AsC 1.928, CCl 1.736 Å; CAsC 107.3, CAsO 111.6°. The packing modes in I and II are significantly different: in I supersymmetrical relationships between the molecules independent of space-group symmetry are found: in II cylindrical cavities of diameter ca. 5 Å are present along the 63 axes. The structures of the molecules in I and II are compared with that of tris(p-chlorophenyl)arsinsulfide, C18H12AsSCl3 (III, space group P21/b, Z = 4). 相似文献
12.
A.A. Pasynskii Yu.V. Skripkin I.L. Eremenko V.T. Kalinnikov G.G. Aleksandrov V.G. Andrianov Yu.T. Struchkov 《Journal of organometallic chemistry》1979,165(1):49-56
(C5H5)2NbBH4 reacts with C5H5M(CO)3Me in toluene solution in the presence of Et3N to give binuclear complexes (C5H5)2NbM(CO)3C5H5 where M is Mo or W (IV and V, respectively). The structure of IV has been studied by X-ray diffraction (the crystals are orthorhombic, a 12.748(5), b 16.745(6), c 14.314 ;; Z = 8, space group of Pbca, automatic difractometer Syntex P2I, λ(Mo-Kα, 1382 reflections, R = 0.056, Rw = 0.058). Molecule IV contains a wedge-like sandwich (π-C5H5)2Nb (NbC 2.37–2.48, CC (av) 1.42 ;, angle between ring planes 49°) linked with the (π-C5H5)Mo(CO) fragment by a direct NbMo bond (3.073 ;) and two bridging CO groups, one nonsymmetrically bonded through the carbon atom only (CO 1.17, NbC 2.53, MoC 2.02 ;) and the other σ-bonded to Mo (MoC 1.944 ;) and π-bonded to Nb (CO 1.22, NbC 2.22, NbO 2.26 ;). Three types of carbonyl groups present in IV give rise to strong IR bands at 1870, 1700 and 1560 cm?1 assigned to the terminal, μ-bridging and σ, π-bridging CO groups respectively. Complex IV has a similar structure. The electronic structure of IV and its dissociation across the NbMo bond are discussed. 相似文献
13.
T.V. Baukova Yu.L. Slovokhotov Yu.T. Struchkov 《Journal of organometallic chemistry》1981,221(3):375-384
The trinuclear cationic complex [Ph4C5(AuPPh3)3+[BF4]- (I) obtained by interaction of C5HPh4AuPPh3 or Ph4C5(AuPPh3)2 with [AuPPh3+[BF4]- in THF was studied by X-ray diffraction. In the presence of benzene, triclinic crystals of the solvate [Ph4C5(AuPPh3)3]+[BF4]-· 2 C6H6 are formed, a = 12.845(6), b = 16.042(8), c = 22.642(11) Å, α = 86.62(4), β = 77.51(4), γ = 76.05(4)°, space group P, Z = 2, 9494 reflections with I > 2σ (λ(Mo-Kα), θ/2θ scan, 2θ < 46°), with absorption correction R = 0.054. The complex represents a diaurated cation of tetraphenylcyclopentadienyl(triphenylphosphine)gold, containing a triangular Au2C fragment (AuAu 2.820(1) Å) which is bonded to the third Au atom (AuAu 3.021(1) Å), coordinated to the cyclopentadienyl ligand by a bond intermediate between η1(σ) and η3 (AuC 2.21(2), 2.60(2) and 2.71(2) Å). 相似文献
14.
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
15.
Crystals of oxo-bis[tribenzylgermanium(IV)], O[(PhCH2)3Ge]2, are rhombohedral, space group R, having a = 9.621(2) Å, α = 85.48(3)°. The structure was solved by Patterson methods using diffractometer data and refined by full-matrix least squares to R = 0.0876. The structure consists of molecules lying along the 3-fold axis of the unit cell, in which the GeOGe fragments are strictly linear and centrosymmetric. The GeO distance is 1.730(1) Å and the GeC distance is 1.980(5) Å. 相似文献
16.
Walter K. Dean Gary L. Simon Paul M. Treichel Lawrence F. Dahl 《Journal of organometallic chemistry》1973,50(1):193-207
The accidental but intriguing synthesis of acetatobis(triphenylphosphine)dicarbonylmanganese(I), (CH3CO2)Mn(CO)2[P(C6H5)3]2, has been accomplished by the reaction of NaMn(CO)5 with (CH3)3SiCl followed by the addition of triphenylphosphine and acetic acid. A three-dimensional single-crystal X-ray diffraction analysis has shown an octahedral-like molecule containing a symmetrically oxygen-chelating acetate group, the first such group to be reported in a metal carbonyl complex. The two triphenylphosphine ligands occupy mutually trans positions with the two carbonyl ligands possessing the remaining cis sites in the octahedral complex. The compound crystallizes with four molecules in a monoclinic unit cell of space group symmetry and of dimensions a = 17.744(2) Å, b = 9.692(1) Å, c = 20.004(2) Å, and β = 106.195(4)°. The relatively long MnO(acetate) bond lengths [2.066(6) and 2.069(7) Å] and the relatively short MnCO bond lengths [1.701(12) and 1.760(13) Å] and the relatively short MnP(C6H5)3 bond lengths [2.260(3) and 2.275(3) Å], compared to the corresponding MnCO and MnP(C6H5)3 bond lengths in other manganese carbonyl triphenylphosphine complexes, are rationalized on the basis that the acetate ligand in this molecule functions primarily as a σ-donor. 相似文献
17.
The molecular geometry of perfluoro(methyloxirane) has been studied using gas-phase electron diffraction data, effective least-squares refinement of the structure being achieved with the aid of constraints to limit the number of variable parameters. With the CCF3 bond constrained to be 0.078 Å longer than the ring CC, the refined bond- length values CF (av.) = 1.323(2), CO (av.) = 1.410(8), and CC (ring) = 1.467(7) Å (g values, with e.s.d. in parentheses) were obtained; the angles between ring bonds and substituent CF bonds were CCF (av.) 121(1) and OCF (av.) 114(1)o, the corresponding parameters involving the bulkier CCF3 fragment being larger by 3o in each case [∠CCCF3 124(1)o∠OCCF3 117(2)o]. The remaining refined parameters were ∠CCF(of CF3) = 110.6(4)o and τ , a torsion angle defining the orientation of the CF bonds of the CF3 group with respect to ring bonds, = 29(2)o. Dependent bond angles possessed the values 62.7 (COC), 58.7 [OCC (ring)], 108.3 [FCF (CF3 group)], 114 [FCF (ring CF2)], and 111o (FCCF3). 相似文献
18.
A.G. Osborne A.J. Blake R.E. Hollands R.F. Bryan S. Lockhart 《Journal of organometallic chemistry》1985,287(1):39-47
A series of [3]ferrocenophanes of general formula Fe(C5H4X)2YCl2 and the spiro compounds [Fe(C5H4X)2]2Ge (X = S, Se; Y = Ge, Sn) have been prepared by the reaction of ferrocene 1,1′-dithiol and ferrocene 1,1′-diselenol with tetrahalides of germanium and tin. Spectroscopic properties of the compounds are reported. In solution, the compounds are fluxional by a bridge reversal process. The crystal structure of 1,3-diselena-2,2-dichlorogermyl-[3]ferrocenophane at 163 K. has been determined by X-ray diffraction methods. At that temperature, crystals have space group P21/n with a 6.222(3), b 16.156(13), c 12.968(4) Å, β 97.53(1)° and Z = 4. Least-squares refinement gave R = 0.033 for 2834 unique significant reflections whose intensities were measured by counter diffractometry. The two SeGe bond lengths are 2.323 and 2.325(1) Å, with GeCl 2.148 and 2.161(1) Å. The SeGeSe bond angle is 118.2(1)°, ClGeCl 104.7(1)°, and SeGeCl angles range from 106.2 to 109.8(1)°. The SeC bond lengths are 1.901 and 1.904(5) Å, with CSeGe angles of 95.8 and 96.5(2)°. The cyclopentadienyl rings are in an eclipsed conformation with a mean twist angle of 2.7°, and are inclined to one another at 6.1°. The Se atoms are displaced from the ring planes by 0.17 and 0.20 Å yielding a non-bonded intramolecular Se…Se contact of 3.99 Å. 相似文献
19.
A.A. Pasynskii Yu.V. Skripkin V.T. Kalinnikov M.A. Porai-Koshits A.S. Antsyshkina G.G. Sadikov V.N. Ostrikova 《Journal of organometallic chemistry》1980,201(1):269-281
CpFe(CO)2CH3 reacts with Cp2NbH made from Cp2NbBH4 and Et3N to give Cp2e (III). As shown by X-ray diffraction, III contains the Cp2NbH sandwich fragment with a 46.8° angle between the rings linked with the dicarbonyliron moiety by the NbFe bond (2.968 Å), observed for the first time, and a cyclopentadienyl bridge C5H4, involving the NbC. σ-bond (2.189 Å) and C5H4Fe π-bond (2.085 Å). A probable reaction scheme leading to III and general patterns of formation of other heterobinuclear derivatives of sandwich complexes Cp2MLM′(L′)n are discussed. The importance of steric effects due to nonbonded interligand interactions between the M′(L′)n fragment and the sandwich system is emphasized. Increase of steric strain in the binuclear system facilitates its unusual transformations. 相似文献
20.
E.B. Lobkovskii G.L. Soloveichik A.I. Sisov B.M. Bulychev A.I. Gusev N.I. Kirillova 《Journal of organometallic chemistry》1984,265(2):167-173
The structure of a titanium aluminium hydride complex of composition [(C5H5)2TiAlH4]2(CH3)2NC2H4N(CH3)2C6H6 has been determined by X-ray diffraction. The complex forms triclinic crystals with unit cell dimensions a = 8.406(2), b = 10.117(2), c = 11.269(3) Å; α = 112.01(2)°, β = 109.25(2)°, γ = 87.04(2)°, space group P, Z = 2 and density d = 1.21 g/cm3. The structure was refined to give a discrepancy index R = 0.056. The crystals are composed of centrosymmetric molecules of (Cp2TiAlH4)2TMEDA (Cp = η5-cyclopentadienyl) and molecules of crystal benzene. Two moieties of Cp2TiH2AlH2 are linked by a tetramethylethylenediamine molecule (rAlN 2.11 Å). The aluminium atom is bonded to a titanium atom by a double hydride bridge (rAlH b = 1.8, 1.6 Å, rTiH b = 1.6 Å), and has trigonal bipyramidal stereochemistry, [H4N] (rAlH t = 1.6 Å). 相似文献