Tethered silyl complexes from nucleophilic substitution reactions at the Si-Cl bond of the chloro(diphenyl)silyl ligand in Ru(SiClPh2)(κ-S2CNMe2)(CO)(PPh3)2

Crystal structure determination of RuH(κ²-S₂CNMe₂)(CO)(PPh₃)₂ (1) confirms that the triphenylphosphine ligands are arranged mutually trans. 1 reacts readily with HSiClPh₂ to eliminate H₂ and produce the six-coordinate silyl complex, Ru(SiClPh₂)(κ²-S₂CNMe₂)(CO)(PPh₃)₂ (2). Crystal structure determination of 2 reveals the same geometrical arrangement of ligands as in 1 with the silyl ligand replacing the hydride ligand. The chloride bound to silicon in 2 is replaced through reactions with 2-hydroxypyridine, 2-aminopyridine, and thallium acetate, producing, respectively, the mono-PPh₃ complexes, Ru(κ²(Si,N)-SiPh₂OC₅H₄N)(κ²-S₂CNMe₂)(CO)(PPh₃) (3), Ru(κ²(Si,N)-SiPh₂NHC₅H₄N)(κ²-S₂CNMe₂)(CO)(PPh₃) (4), and Ru(κ²(Si,O)-SiPh₂OCMeO)(κ²-S₂CNMe₂)(CO)(PPh₃) (5). Crystal structure determinations of 3, 4, and 5 confirm that in each case there is formation of a five-membered chelate ring tethering the silyl ligand to ruthenium. In the formation of 3, 4, and 5 the Si-ligand and the two S atoms of the dimethyldithiocarbamate ligand remain meridional but the remaining triphenylphosphine ligand and the carbonyl ligand are interchanged in position leaving the donor atom of the tether trans to the CO ligand. An alternative way of considering the tethered silyl ligands in 3, 4, and 5 is as tethered, base-stabilised, silylene ligands and the structural data give some support for a contribution from this bonding model.     

The structurally characterised silyl complexes, Os(κ-S2CNMe2)(SiMeCl2)(CO)(PPh3)2 and Os(κ-S2CNMe2)(SiCl3)(CO)(PPh3)2, which have remarkably unreactive Si-Cl bonds

Treatment of Os(κ²-S₂CNMe₂)H(CO)(PPh₃)₂ with HSiMeCl₂ or HSiCl₃ gives in high yield Os(κ²-S₂CNMe₂)(SiMeCl₂)(CO)(PPh₃)₂ (1) or Os(κ²-S₂CNMe₂)(SiCl₃)(CO)(PPh₃)₂ (2), respectively. The crystal structures of both compounds have been determined and the Os-Si distances are 2.3672(10) Å for 1 and 2.3449(12) Å for 2. In solution, and under forcing conditions, both compounds are extraordinarily unreactive towards hydroxide ions.     

Reactions of the titanium-carbide species CpTi(μ-Me)(μ-NPi-Pr3)(μ-C)(AlMe2)3

The reaction of CpTi(μ²-Me)(μ²-NPi-Pr₃)(μ⁴-C)(AlMe₂)₃ with ClSnMe₃ and MeO₃SCF₃ affords the species CpTi(μ²-Cl)(μ²-NPi-Pr₃)(μ⁴-C)(μ²-Cl)(AlMe)(AlMe₂)₂1 and CpTi(μ²-Me)(μ²-NPi-Pr₃)(μ⁴-C)(μ²-O₃SCF₃)(AlMe)(AlMe₂)₂2, respectively. Both 1 and 2 have been structurally characterized.     

Stable radical adducts of diisopropylphosphoryl radicals with fullerene complexes (η2-C60)Os(CO)(PPh3)2(CNBut) and (η2-C70)Os(CO)(PPh3)2(CNBut)

It was determined by ESR spectroscopy that the UV irradiation of toluene solutions containing Hg[P(O)(OPrⁱ)₂ and the complex (²-C₆₀)Os(CO)(PPh₃)₂(CNBu^t) produces six stable regioisomeric adducts of phosphoryl radicals with complexes, which are not demetallated under UV irradiation and do not dimerize in the absence of UV irradiation. This is caused by the addition of the phosphoryl radicals to the carbon atoms of fullerene localized near the metal-containing moiety. The addition of the phosphoryl radicals to (²-C₇₀)Os(CO)(PPh₃)₂(CNBu^t) gives rise to the formation of nine stable regioisomeric radical adducts. A comparison of the composition of regioisomers of the radical adducts of C₇₀ with the phosphoryl radicals, which were formed directly from C₇₀ and from the radical adducts of ²-C₇₀)Os(CO)(PPh₃)₂(CNBu^t) by the demetallation of the latter, revealed an orienting effect of the osmium-containing moiety on the addition of the phosphoryl radicals to the fullerene complex.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1968–1972, September, 2004.     

The bis(trifluoroacetate) analogue of the first-generation Grubbs catalyst: Synthesis, X-ray structure, and metathesis activity of [Ru(CF3CO2)(η-CF3CO2)(CHPh)(PCy3)2]

A simple synthesis of [Ru(CF₃CO₂)(η²-CF₃CO₂)(CHPh)(PCy₃)₂] from dimeric [Ru₂(CF₃CO₂)₂(μ-CF₃CO₂)₂(CHPh)₂(PCy₃)₂(μ-H₂O)] is described. The new complex crystallizes in monoclinic system (P2(1)/c space group) with distorted octahedral coordination. The very low metathesis activity of this new ruthenium benzylidene complex demonstrates that substitution of chlorides with trifluoroacetates in [RuCl₂(CHPh)(PCy₃)₂] results in loss of the catalytic activity.     

Thiolate-bridged heterometallic complexes of manganese and platinum: Synthesis and molecular structures of (CO)4Mn(μ-SPh)Pt(PPh3)2, (CO)3(PPh3)Mn(μ-SPh)Pt(PPh3)(CO), and (CO)3Mn(μ-SPh)Pt(PPh3)(Dppm)

A reaction of the dimer [Mn(CO)₄(SPh)]₂ with (PPh₃)₂Pt(C₂Ph₂) gave the heterometallic complex (CO)₄Mn(μ-SPh)Pt(PPh₃)₂ (I) and its isomer (CO)₃(PPh₃)Mn(μ-SPh)Pt(PPh₃)(CO) (II). A reaction of complex I with a diphosphine ligand (Dppm) yielded the heterometallic complex (CO)₃Mn(μ-SPh)Pt(PPh₃)(Dppm) (III). Complexes I–III were characterized by X-ray diffraction. In complex I, the single Mn-Pt bond (2.6946(3) ?) is supplemented with a thiolate bridge with the shortened Pt-S and Mn-S bonds (2.3129(5) and 2.2900(6) ?, respectively). Unlike complex I, in complex II, one phosphine group at the Pt atom is exchanged for one CO group at the Mn atom. The Mn-Pt bond (2.633(1) ?) and the thiolate bridge (Pt-S, 2.332(2) ?; Mn-S, 2.291(2) ?) are retained. In complex III, the Mn-Pt bond (2.623(1) ?) is supplemented with thiolate (Pt-S, 2.341(2) ?; Mn-S, 2.292(2) 0?) and Dppm bridges (Pt-P, 2.240(1)?; Mn-P, 2.245(2) ?). Apparently, the Pt atom in complexes I–III is attached to the formally double bond , as in Pt complexes with olefins.     

First example of ruthenium nitroso monoammine complex. Crystal structure of [Ru(NO)(NH3)3(H2O)Cl] × [Ru(no)(NH3)3(OH)Cl][Ru(NO)(NH3)Cl4]2Cl·2H2O

The structure of the interaction products of (NH₄)₂[Ru(NO)Cl₅] solution with ammonium acetate on heating is studied. The crystal structure of the [Ru(NO)(NH₃)₃(H₂O)Cl][Ru(NO)(NH₃)₃(OH)Cl] × [Ru(NO)(NH₃)Cl₄]₂Cl-2H₂O compound (compound I) containing a previously unknown anion of the nitrosomonoammine series is determined: Cc space group; a = 33.530(7) ?, b = 8.202(2) ?, c = 11.844(2) ?; β= 101.54(3)°.     

Synthesis and structures of the silyl bridged bis(indenyl) diruthenium complexes and a novel indenyl nonanuclear ruthenium cluster Ru9(μ6-C)(CO)14(μ3-η:η:η-C9H7)2

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 Ru₉(μ₆-C)(CO)₁₄(μ₃-η⁵:η²:η²-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.     

Reactions of the triosmium cluster Os3(μ-H)(μ-OH)(CO)10 with naphthols

Reaction of the cluster Os₃(μ-H)(μ-OH)(CO)₁₀ (1) with 1-naphthol afforded the isomeric clusters 2a and 3a with the formulae Os₃(μ-H)₂(μ₃-1-OC₁₀H₆)(CO)₉. A similar reaction with 2-naphthol, however, gave Os₃(μ-H)(μ-2-OC₁₀H₇)(CO)₁₀, 4b, and the analogue of 2a. These clusters have been structurally characterised to confirm the mode of anchoring of the naphthols.     

［La(CH2ClCOO)2(NO3)(phen)(H2O)］n的合成和晶体结构

合成了混合阴离子配合物［La(CH₂ClCOO)₂(NO₃)(phen)(H₂O)］_n。配合物经元素分析、IR、DTA-TG和UV等表征。用X射线单晶结构分析解析了标题配合物的晶体结构，三斜，空间群P1，晶胞参数为a=10.533(2)?，b=13.136(3)?，c=7.776(1)?，α=96.59(1)°，β=95.76(1)°，γ=108.42(2)°，V=1003.3(3)?³，Z=2,Dc=1.940 g/cm³, F(000)=572, μ(Mo Kα)=24.36 cm^-1。     

Structure and synthesis of nitrosoruthenium trans -diammines [Ru(NO)(NH3)2Cl3] and [Ru(NO)(NH3)2(H2O)Cl2]Cl·H2O

A DTA study of thermal decomposition of (NH₄)₂[Ru(NO)Cl₅] in helium atmosphere has been carried out, a synthetic procedure for preparation of the trans-diammine complex mer-[Ru(NO)(NH₃)₂Cl₃] (I) with yield ∼70% has been developed. On re-crystallization of I from aqueous solution a trans-aquanitroso complex [Ru(NO)(NH₃)₂Cl₂(H2O)]Cl·H₂O (II) has been isolated. The structures of the compounds have been determined by single crystal X-ray diffraction: space group Pbcn, a = 6.607(1) ? b = 11.255(2) ? c = 9.878(2) ? (I) and space group Ima2, a = 8.3032(3) ?, b = 8.0890(2) ?, c = 15.9192(5) ? II). Original Russian Text Copyright ? 2008 by M. A. Il’in, V. A. Emel’yanov, and I. A. Baidina __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 6, pp. 1128–1136, November–December, 2008.     

铂氢化物trans-[PtH(tu)(PPh3)2]Cl(tu)(THF)2(tu=SC(NH2)2)的结构

制得含硫脲配体的铂氢化物单晶trans-[PtH(tu)(PPh₃)₂]Cl(tu)(THF)₂,其结构测定结果为:C₄₆H₅₅N₄O₂P₂S₂ClPt M=1052.6,单斜晶系,空间群为 P2₁/c,a=12.103(1),b=21.619(3),c=20.189(4)Å,β=103.31(0)°,V=5140(2)ų,Z=4,D_c=1.360g·cm^-3,F(000)=2128,R=0.050,R_w=0.063.Pt(Ⅱ)与两个磷、一个硫脲分子的硫和一个氢相配合,形成四边形配位。     

Novel chromium trinuclear trifluoroacetate complexes Cr3(μ3-O)(CF3COO)6(CH3COOH)2(CF3COO) and Cr3(μ3-O)(CF3COO)6(CH3COOH)2(THF): Synthesis and crystal structure

Novel anhydrous trinuclear ₃-oxo complexes of Cr(III), Cr₃(₃-O)(CF₃COO)₆(CH₃COOH)₂(CF₃COO) (I) and of Cr(III,III,II), Cr₃(₃-O)(CF₃COO)₆(CH₃COOH)₂(THF) (II) (where THF is (CH₂)₄O) are synthesized by anodic dissolution of metallic chromium in solutions of trifluoroacetic acid in acetonitrile and in tetrahydrofuran and their structures are studied by X-ray diffraction analysis. Complex I forms orthorhombic crystals with space group Pna2₁, a = 9.778(1) , b = 16.042(2) , c = 22.851(4) , Z = 4, R ₁ = 0.0332; complex II crystallizes in monoclinic system: space group P2₁/c, a = 9.866(1) , b = 17.895(2) , c = 21.167(4) , = 100.75(2)°, Z = 4, R = 0.0422. The average Cr-(₃-O) distances in compounds I and II are almost equal (1.943(3) and 1.927(3) ). An average length of the Cr-O bond in octahedral surrounding of metal atoms is different in complexes I and II (1.985(4) and 2.003(3) , respectively), which is specified by different oxidation states of the metal atom. The CrCr distances lie in an interval of 3.366(1)–3.337(1) .__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 4, 2005, pp. 266–272.Original Russian Text Copyright © 2005 by Glazunova, Boltalin, Troyanov.     

Reactivity of [Os3(CO)10(NCMe)2] and [Os3(CO)10(μ-Cl)(μ-AuPPh3)] with 4-mercaptopyridine: X-ray structure of [Os3(CO)10(μ-H)(μ-SC5H4N)] and [Os3(CO)10(μ-AuPPh3)(μ-SC5H4N)]

The compound [Os₃(CO)₁₀(μ-Cl)(μ-AuPPh₃)] (2) was prepared from the reaction between [Os₃(CO)₁₀(NCMe)₂] (1) and [AuClPPh₃] under mild conditions. The reaction of 2 with 4-mercaptopyridine (4-pyS) ligand yielded compounds [Os₃(CO)₁₀(μ-H)(μ-SC₅H₄N)] (4), formed by isolobal replacement of the fragment [AuPPh₃]⁺ by H⁺ and [Os₃(CO)₁₀(μ-AuPPh₃)(μ-SC₅H₄N)] (5). [Os₃(CO)₁₀(μ-H)(μ-SC₅H₄N)] (4) was also obtained by substitution of two acetonitrile ligands in the activated cluster 1 by 4-pyS, at room temperature in dichloromethane. Compounds 2-5 were characterized spectroscopically and the molecular structures of 4 and 5 in the solid state were obtained by single crystal X-ray diffraction studies.     

The preparation and crystal structure of (η-C5H5)(OC)3Mo(CH2)3C6H5

The reaction of with p-CH₃C₆H₄S(O)₂O(CH₂)₃C₆H₅ produces (η⁵-C₅H₅)(OC)₃Mo(CH₂)₃C₆H₅. This is only the second structurally characterized organometallic species in which an aromatic moiety is separated by three or more methylene groups. The alkyl chain adopts a staggered conformation, the Mo-C(1)-C(2)-C(3)-C(4) unit is nearly coplanar, and the alkyl chain eclipses the trans-carbonyl group on Mo. NMR evidence indicates that this conformation is preserved in solution.     

Crystal structure of Sm(Phen)(i-Bu2PS2)3·MeCN and photoluminescence properties of SmL(i-Bu2PS2)3 (L = Phen, 2,2′-bipy)

It is revealed that at 300 K Sm(Phen)(i-Bu₂PS₂)₃ (I) and Sm(2,2′-Bipy)(i-Bu₂PS₂)₃ (II) complexes have photoluminescence properties typical of the Sm³⁺ ion. In the spectra, three bands are observed with 7n_max = 564 nm, 600 nm, and 645 nm. Single crystals of Sm(Phen)(i-Bu₂PS₂)₃·MeCN (III) are grown, and the structure of the compound is determined based on the X-ray diffraction data (X8 Apex diffractometer, MoK6h radiation, 7685 F _hkl, R = 0.0258). Crystals of III are triclinic, unit cell parameters are a = 11.0554(3) ?, b = 15.0446(3)?, c= 15.4849(4)?; 6h = 89.218(1)°, β = 75.555(1)°, γ = 73.484(1)°, V= 2386.6(1)?³, Z=2, ρ_calc = 1.391 g/cm³, P1 space group. The structure of III is formed from the molecules of mononuclear complex I and MeCN molecules. A coordination polyhedron of the Sm atom is an N₂S₆ tetragonal antiprism. It is shown that the structure of III includes dimeric assemblies of the molecules of complex I.     

A new coordination mode for (pyrid-2-yl)thiolate (L) ligands: Synthesis and characterization of [Ru6(μ3-H)(μ5-κ-L)(μ-CO)(CO)15]

The hexaruthenium cluster complexes [Ru₆(μ₃-H)(μ₅-κ²-L)(μ- CO)(CO)₁₅], HL = 2-mercaptopyridine (1) and 2-mercapto-6-methylpyridine (2), have been prepared by heating [Ru₃(CO)₁₂] with 0.5 equiv. of HL in THF at reflux temperature. An X-ray diffraction study on a crystal of complex 2 has determined that its metallic skeleton, a basal-edge-bridged square pyramid, is hold up by a (6-methylpyrid-2-yl)thiolate ligand. This ligand is attached to the four basal ruthenium atoms of the pyramid through the sulfur atom and to the edge-bridging ruthenium atom through the nitrogen atom. Such a coordination mode is unprecedented for (pyrid-2-yl)thiolate ligands.     

Synthesis of electronically and coordinatively unsaturated complexes [Ru2(CO)4(μ-H)(μ-PBu2)(μ-L2)] (L2 = biphosphanes)

A convenient synthesis and the characterization of six new electronically and coordinatively unsaturated complexes of the formula [Ru₂(CO)₄(μ-H)(μ-P^tBu₂)(μ-L₂)] (2b-g) (RuRu) is described exhibiting a close relation to the known [Ru₂(CO)₄(μ-H)(μ-P^tBu₂)(μ-dppm)] (2a). The complexes 2b-g were obtained in a kind of one-pot synthesis starting from [Ru₃(CO)₁₂] and P^tBu₂H in the first step followed by the reaction with the bidentate bridging ligand in the second step. The method was developed for the following bridging ligands (μ-L₂): dmpm (2b, dmpm = Me₂PCH₂PMe₂), dcypm (2c, dcypm = Cy₂PCH₂PCy₂), dppen (2d, dppen = Ph₂PC(=CH₂)PPh₂), dpppha (2e, dpppha = Ph₂PN(Ph)PPh₂), dpppra (2f, dpppra = Ph₂PN(Pr)PPh₂), and dppbza (2g, dppbza = Ph₂PN(CH₂Ph)PPh₂). The molecular structures of all new complexes 2b−g were determined by X-ray diffraction.     

Syntheses and molecular structures of Ru3(μ-H)(μ3-CPh2CCCCPh)(CO)9 and Ru3{μ3-CPhCHCC(CPh2)CHCPh}(μ-CO)(CO)8

The reaction between Ru₃(μ-H){μ₃-C₂CPh₂(OH)}(CO)₉ and HCCPh, carried out in the presence of HBF₄ · Me₂O, afforded the cluster complexes Ru₃(μ-H)(μ₃-CPh₂CCCCPh)(CO)₉ (5) and Ru₃{μ₃-CPhCHCC(CPh₂)CHCPh}(μ-CO)(CO)₈ (6), both of which were characterised by single-crystal X-ray studies.