Reactions between 8-quinolinol (and related ligands) and triruthenium dodecacarbonyl; x-ray crystal structure determination of Ru3(CO)8(C9H6NO)2

8-Quinolinol reacts with Ru₃(CO)₁₂ to give Ru₃(CO)₈(C₉H₆NO)₂ and Ru- (CO)₂(C₉H₆NO)₂. A single-crystal X-ray study of the cluster compound shows that the three ruthenium atoms define an isosceles triangle, with two distances of 2.77 Å and one of 3.04 Å. Since both metalated oxygens act as three-electron donors (RuO distances 2.12 and 2.18 Å), the cluster is a fifty-electron species with a formal zero bond order for the elongated RuRu bond. Four other hydroxyhydrocarbylpyridine compounds also give complexes of composition Ru₃(CO)₈(L)₂ which probably have analogous structures.     

Kristall- und molekülstruktur von hexaphenyldistannylselenid (C6H5)3SnSeSn(C6H5)3

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: SnSe 2.526 (2.521(3) ? 2.538(3)) Å; SnC 2.138 (2.107(16)?2.168(19)) Å; SnSeSn 103.4(1)°, 105.2(1)°. There are only slight angular distortions at the SnSeC₃ tetrahedra (SeSnC angles: 104.3(5)?114.8(4)°). The bond data indicate essentially single bonds around the Sn atoms.     

Kristall-und molekülstrukturen zweier modifikationen de hexaphenyldigermylsulfids (C6H5)3GeSGe(C6H5)3

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: GeS 2.212(1) and 2.261(1) » (2.227(2) and 2.240(2) »); GeC 1.933(4) ? 1.971(4), mean 1.945(5) » (1.931(7)?1.954(7), mean 1.943(4) »); GeSGe 111.2(1)° (110.7(1)°). The Ge bond lenghts are comparable to those in thiogermanates and do not indicate significant π-bond contributions.     

H-transfer catalysis with Ru3(CO)12

Ru₃(CO)₁₂ , in the presence of tolane, catalyzes the formation of esters from the following three systems: alcohol + aldehyde, alcohol and aldehyde.     

Synthesis and reactivity of [N(C6H4Br)3][B(C6F5)4]: the X-ray crystal structure of [Fe(C5H5)2][B(C6F5)4]

A new chemical oxidant [N(4-C₆H₄Br)₃][B(C₆F₅)₄], was prepared and used to synthesize [Fe(C₅H₅)₂][B(C₆F₅)₄]. The crystal structure of [Fe(C₅H₅)₂][B(C₆F₅)₄] was determined.     

Etude vibrationnelle des composes (C4H4P)Mn(CO)3 et [C4H2(CH3)2P]Mn(CO)3 et calcul du champ de force du cycle C4H4P complexe

The Raman and infrared spectra (4000200 cm^?1) of (C₄H₄P)Mn(CO)₃ and (C₄D₄P)Mn(CO)₃, and of [C₄H₂(CH₃)₂P]Mn(CO)₃ and [C₄D₂(CH₃)₂P]Mn(CO)₃ in the liquid and solid states (10–400 K) have been investigated. A complete vibrational assignment is proposed and valence force fields of the (C₅H₅) and (C₄H₄P) cycles are compared. From these results, it is clearly shown that the (C₄H₄P) rings are more electrophilic and weaker π-electron donors than (C₅H₅) rings, this is in agreement with their chemical behavior.     

Reaction of Ru3(CO)12 with styrene

The reaction of styrene with Ru₃(CO)₁₂ yields the known complex Ru₄(CO)₁₂(PhCCH) and the new cluster Ru₄(CO)₉(PhCCH)(PhEt), in which a second molecule of styrene is hydrogenated and η⁶-bonded.     

Solubility of trans-Co2(CO)6 [3,5-bis(CF3)C6H3P(i-C3H7)2] in dense carbon dioxide

The title compound (1) was prepared by the reaction of 3,5-bis(CF₃)C₆H₃P(i-C₃H₇)₂ (L1) and Co₂(CO)₈. Its solubility in supercritical carbon dioxide was measured at varying temperatures and pressures using a modified analytical extraction device. Solubility data were determined in the temperature and pressure ranges between 40 and 70 °C and between 100 and 300 bar, respectively. The solubility of 1 is lower compared to (p-CF₃C₆H₄)₃P, but much higher than for transition metal complexes bearing phosphines without fluorinated substituents.     

Fe3(CO)8(C6H5NC)(μ3-S)2的合成和晶体结构

The title compound Fe_3(CO)_8(C_6H_5NC)(μ_3-S)_2 (Ⅰ) was synthesized by the reaction of C_6H_5NCS with Fe_3(CO)_12 at room temperature. The crystal and molecular structure of the title compound were determined by single ctystal diffraction method. Crystal data: monoclinic, space group P2_1/C, a=12.718(4)Å, b=26.164(10) Å, c=l3.741(7) Å, β=117.18(2) °, V=4067(2) Å3, Z=8, Dc=1.825 g/cm3. The structure was solved by direct method and difference Fourier synthesis, and refined by full-matrix Least-squares with anisotropic thermal paramaters, using 1990 observed reflections [Ⅰ＞3σ(Ⅰ)].The final residual factor was R＝0.076, Rw＝0.082. The substituted ligand (C_6H_5NC)in Fe_3(CO)_8(C_6H_5NC)(μ_3-S)_2 is connected to the Fe(3) atom of the distorted tetragonal pyramid Fe_3S_2 framework.     

The crystal and molecular structure of dicarbonylbis(diphenylethylphosphine) platinum(0) Pt(CO)2[P(C6H5)2(C2H5)]2

The complex dicarbonylbis(diphenylethylphosphine)platinum, Pt(CO)₂[P(C₆H₅)₂(C₂H₅)]₂, crystallizes in either of the enantiomorphous space groups P3₁21 (No. 152) and P3₂21 (No. 154) with cell dimensions a = 10.64(1), c = 22.06(1) Å, U = 2163 ų; p_c = 1.564 g/cm³ for Z = 3, p_m = 1.55(3) g/cm³. The intensities of 1177 independent reflections have been determined by counter methods with MoKα monochromatized radiation. The structure has been solved by the heavy atom method. The refinement, carried out by full-matrix least squares down to a final R factor of 0.042, has enabled the absolute configuration of the crystal sample (space group P3₁21) to be ascertained. The molecule is roughly tetrahedral, and has the metal atom lying on a two-fold axis of the cell. Bond parameters are: PtC = 1.92(2) Å, PtP = 2.360(4) Å, CPtC = 117(1)° and PPtP = 97.9(2)°. The PtC₂ and PtP₂ moieties make a dihedral angle of 86.0(3)°. The overall C₂ symmetry of the molecule is probably only a statistically averaged situation, a disorder in the PtCO interactions being apparent from the orientations of the thermal ellipsoids of the C and O atoms.     

A localized molecular orbital study on the bonding of> Mo3S4]2Mo> and> Mo3S4]CuI> versus (C6H6)2Cr and C6H6Cr(CO)3

The energy-localized CNDO/2 molecular orbitais have been calculated for the clusters containing molybdenum, > {Mo₃S₄₂Mo}⁸⁺ and> Mo₃S₄]CuI> ⁴⁺, versus the prototype arene-metal sandwich (C₆H₆)₂Cr and half-sandwich complexes C₆H₆Cr(CO)₃. The bonding characteristics of these compounds are described from a localization bonding viewpoint. There are two typical M-arene and M-[Mo₃S₄] bondings. One is formed by electron donation from the three-center two-electron π-bonds in the arene or [Mo₃S₄]⁴⁺ ligands into the vacant hybrid orbitais of the “stranger” metal atom. In the other M-arene or M-[Mo₃S₄] bond there is very little donation by the lone electron pair occupying the d AOs of the “stranger” metal atom to the arene or [Mo₃S₄]⁴⁺ ligands. The analogy of the ligand [Mo₃S₄]⁴⁺ in the clusters studied with the ligand benzene is also briefly discussed.     

Syntheses and structural studies on two cycloruthenapentadienyl complexes: [(CO)3RuC4(CH2OH)4]Ru(CO)3·H2O and [(CO)3RuC4(CH2CH2OH)2(C2H5)2]Ru(CO)3

Syntheses and single-crystal X-ray diffraction studies have been completed on two cycloruthenapentadienyl (CO)₆Ru₂L₂ derivatives, with L = CH₂OHC = CCH₂OH and C₂H₅C=CCH₂CH₂OH respectively. Crystal data are as follows: for [(CO)₃RuC₄(CH₂OH)₄]Ru(CO)₃·H₂O, P2₁/c, a 13.72(1), b 9.501(4), c 14.86(1) Å, β 101.10(6)°, R_w = 0.052 for 1911 reflections; for [(CO)₃RuC₄(CH₂CH₂OH)₂(C₂H₅)₂]Ru(CO)₃, P2₁/c, a 9.191(3), b 16.732(4), c 14.903(3) Å, β 113.61(4)°, R_w = 0.042 for 2865 reflections. Both compounds are built up from binuclear units, each unit being regarded as a Ru(CO)₃ fragment π-bonded to a cycloruthenapentadienyl ring. The molecular parameters are compared with those of known cyclometallapentadienyl complexes of transition metals. The presence of a semi-bridging CO group is discussed.     

Cis-trihetero-tris-σ-homobenzenes as tridentate ligands - X-ray crystal. Structure analyses of the Co(C6H9N3)2(NO3)3 and Ba(C6H6O3)4(ClO4)2-complexes

According to X-ray crystal structure analyses “cis-benzenetrisimine” ($\text{2}$) and “cis-benzenetrioxide” ($\text{1}$) act as tridentate ligands in their 2:1- and 4:1-complexes $\text{7}$ (Co(C₆H₉N₃)₂(NO₃)₃) and $\text{8}$ (Ba(C₆H₆O₃)₄(ClO₄)₂), resp. The latter is the rare example of an organic complex with the (approximate) T-symmetry.     

Die thermische reaktion von C5H5(CO)2FeNa mit benzimidchloriden C6H5(Cl)CNR

η⁵-C₅H₅(CO)₂FeNa reacts with the benzimide chlorides C₆H₅(Cl)CNR (R  CH(CH₃)₂, C₆H₅) in boiling THF to give the η¹-iminoacyl complexes η⁵-C₅H₅ (CO)₂Fe[η¹-C(C₆H₅)NR]. Alternatively, the new Fe complexes [η⁵-C₅H₅(CO)Fe$\text{C(C}{}_6\text{H}{}_5\text{)N(CH}{}_3\text{)C(C}{}_6\text{H}{}_5\text{)N}$CH₃PF₆ (IV) and [η⁵-C₅H₅(CO)₂FeC(C₆H₅)N(CH₃)C(C₆H₅)NCH₃]PF₆ (V) are formed under the same conditions, if R  CH₃. Hudrolysis of the CN single bond of the ligand in V, not stabilized by a chelate effects as in IV, results in the formation of [η⁵-C₅H₅(CO)₂FeC(C₆H₅)NHCH₃]PF₆ (VII). Reaction of η⁵-C₅H₅(CO)₂ with N-benyzylbenzimido chloride yields η⁵-C₅H₅(CO)₂FeCH₂C₆H₅ as the only isolated product.     

Synthesis and structures of triphenylbismuth diaroxides Ph3Bi(OAr)2, Ar = C6H3(Br2-2,4), C6H2(Br2-2,6)(NO2-4), and C6H2[(NO2)3-2,4,6]

Triphenylbismuth diaroxides Ph₃Bi(OAr)₂ (Ar = C₆H₃(Br₂-2,4) (I), C₆H₂(Br₂-2,6)(NO₂-4) (II), and C₆H₂[(NO₂)₃-2,4,6] (III) are synthesized in yields up to 74% by the reaction of triphenylbismuth with phenols in the presence of hydrogen peroxide (taken at a molar ratio 1: 2: 1, respectively) in ether. According to X-ray diffraction data, the bismuth atoms in compounds I-III have distorted trigonal-bipyramidal coordination with the aroxyl substituents in the axial positions; the Bi-C, Bi-O bond lengths and the OBiO, CBiC angles vary in the intervals 2.162–2.204, 2.150–2.299 ? and 172.4°–176.1°, 109.6°–139.9°, respectively. Compound II exhibits intramolecular contacts between the central atom and ortho-Br atoms (3.924, 4.101 ?), and compound III has similar contacts of the Bi atom with the O atoms of the ortho-nitro groups (3.114, 3.313 ?). Original Russian Text ? V.V. Sharutin, I.V. Egorova, O.K. Sharutina, A.P. Pakusina, M.A. Pushilin, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 1, pp. 14–21.     

Photoinduced formation of phosphido-bridged clusters derived from Ru3(CO)9(PPh2H)3. Crystal and molecular structure of Ru3(μ-H)(μ-PPh2)3(CO)7

The new complex Ru₃(CO)₉(PPh₂H)₃ (I) was prepared by the direct thermal reaction of Ru₃(CO)₁₂ with PPh₂ H and was spectroscopically characterized. Irradiation of I with λ ≥ 300 nm leads to the formation of Ru₂(μ-PPh₂)₂(CO)₆ (II) and three new phosphido-bridged complexes, Ru₃(μ-H)₂(μ-PPh₂)₂(CO)₈ (III), Ru₃(μ-H)₂(μ-PPh₂)₂(CO)₇(PPh₂H) (IV) and Ru₃(μ-H)(μ-PPh₂)₃(CO)₇ (V). These complexes have been characterized spectroscopically and Ru₃ (μ-H)(μ-PPh₂)₃(CO)₇ by a complete single crystal X-ray structure determination. It crystallizes in the space group P2₁/n with a 20.256(3), b 22.418(6), c 20.433(5) Å, β 112.64(2)°, V 8564(4) ų, and Z = 8. Diffraction data were collected on a Syntex P2₁ automated diffractometer using graphite-monochromatized Mo-K_α radiation, and the structure was refined to R_F 4.76% and R_wF 5.25% for the 8,847 independent reflections with F₀ > 6σ(F₀). The structure consists of a triangular array of Ru atoms with seven terminal carbonyl ligands, three bridging diphenylphosphido ligands which bridge each of the RuRu bonds, and the hydride ligand which bridges one RuRu bond. Complex IV was also shown to give V upon photolysis and is thus an intermediate in the photoinduced formation of V from I.     

NMR study of (C6H5)3-nPXn (X = Cl,Br, I; n = 0-3) and (C6H6)3-n PXnCr(CO)5 compounds

The ³¹P chemical shift of the (C₆H₅)_3-nPX_n ligands (X = Cl, Br, I; n = 0–3) is dominated by the electronegativity of the substituents. π bonding is only important for derivatives with three strongly electronegative substituents. The ³¹P chemical shift of the corresponding complexes (C₆H₅)_3-nPX_nCr(CO)₅ is governed by the simultaneous effects of the electronegativity, steric hindrance and π bonding. The resonance parameter, δ', indicates an increasing (p_ring → d_p)π and (d_cr→ d_p)π electron delocalization with halogen substitution.     

The PtP(C6H11)3(C2H4)2 mediated activation of aldehyde CH bonds via chelate-assisted oxidative addition reactions

Hydrocarbon solutions of PtPCy₃(C₂H₄)₂ (Cy = cyclohexyl) react rapidly with 8-quinolinecarboxaldehyde (1 equiv.) to yield tricyclohexylphosphine quinolinecarboxyl platinum hydride (1) and CH₂CH₂ (2 equiv.). Compound 1 reacts with CCl₄ in hydrocarbons to give PtPCy₃(NC₉H₆CO)Cl (2) and CHCl₃. The compound PtPCy₃(C₂H₄)₂ also reacts with Ph₂P(C₆H₄-o-CHO) and Ph₂As(C₆H₄-o-CHO) to give PCy₃PtPh₂P(C₆H₄-o-CO)(H) (3) and PCy₃PtPh₂As(C₆H₄-o-CO)(H) (4), respectively. Compounds 1, 2, 3, and 4 were characterized by infrared and ¹H NMR spectra, and the crystal structure of 3 was determined by X-ray diffraction. Crystals of 3 are monoclinic, with space group P2₁/n and Z = 4 with the unit cell dimensions a 9.7936(17), b 14.844(35), c 23.530(64) Å, β 91.817 (18)°, and V 3419.09(1.36) ų. The structure is refined to final discrepancy factors of R = 0.055, and R_w = 0.064. The molecular structure of 3 is that ligating atoms are in a plane containing Pt. The position of the hydride was not located crystallographically, but the ¹H NMR spectrum of 3, supports the presence of a terminal hydride that is cis to the carbonyl. The IR band of 3 at 2023 cm^?1 which is assigned to ν(PtH), and the hydride cleavage reaction of 1 with CCl₄, provide evidence for the PtH bond.     

Neutron scattering study of the reorientational motions in Cr(CO)3(η6C6H6) and Mn(CO)3(η5C5H5)

Incoherent quasi-eleastic neutron scattering experiments: using different resolutions and a wide Q range, have been performed on polycrystalline samples of Cr(CO)₃(η⁶C₆H₆) and Mn(CO)₃(η⁵C₅H₅) in the 280–320 K temperature range. It is shown that aromatic rings are involved into a reorientational process characterized by an activation energy of ≈ 16 kJ mol^?1 and by correlation times of the order of 2 × 10^?11 s and 5 × 10^?11 s at 300 K for C₆H₆ and C₅H₅ rings respectively. Experimental elastic incoherent structure factors are in agreement with the 2π/6 and 2π/5 jump models and the fitted spectra confirm these models. From a comparison with heat-capacity results we conclude that M(CO)₃ groups are fixed during the reorientational process. Finally a comparison with literature data is presented.     

The molecular structure of benzoylmethylidynetricobalt nonacarbonyl,C6H5C(O)CCo3(CO)9

The molecular structure of benzoylmethylidynetricobalt nonacarbonyl, C₆H₅C(O)CCo₃(CO)₉, has been determined by single crystal X-ray crystallography. The sample crystallized from heptane forms as monoclinic prisms of spae group P2₁/c, with a = 8.836(2), b = 14.097(10), c = 16.514(3), β = 103.37(6) and z = 2. The final R value was 0.053. The structure is regular and normal but does not aid in explaining the interesting properties of this cluster.