Mononuclear hydridocarbonyl ruthenium complexes incorporating N2O2 bis-chelating ligands

The reactions of [RuH(CO)Cl(PPh₃)₃] with N,N^′-bis(salicylidine)-hydrazine (H₂bsh) and N,N^′-bis(salicylidine)-p-phenylene diammine (H₂bsp) in presence of KOH in methanol led in the formation of neutral mononuclear complexes with the formulations [RuH(CO)(PPh₃)₂(L)] (LHbsh or Hbsp). These present the first examples where the ligands H₂bsh or H₂bsp provide only two of its available donor sites for interaction with the metal centre. The complexes have been characterized by elemental analyses, FAB-MS, IR, ¹H, ¹³C, ³¹P NMR and electronic spectral studies. Molecular structure of the representative complex [RuH(CO)(PPh₃)₂(Hbsh)] have been determined by single crystal X-ray analysis.     

Iodomethane oxidative addition and CO migratory insertion in monocarbonylphosphine complexes of the type [Rh((C6H5)COCHCO((CH2)nCH3))(CO)(PPh3)]: Steric and electronic effects

The chemical kinetics, studied by UV/Vis, IR and NMR, of the oxidative addition of iodomethane to [Rh((C₆H₅)COCHCOR)(CO)(PPh₃)], with R = (CH₂)_nCH₃, n = 1-3, consists of three consecutive reaction steps that involves isomers of two distinctly different classes of Rh^III-alkyl and two distinctly different classes of Rh^III-acyl species. Kinetic studies on the first oxidative addition step of [Rh((C₆H₅)COCHCOR)(CO)(PPh₃)] + CH₃I to form [Rh((C₆H₅)COCHCOR)(CH₃)(CO)(PPh₃)(I)] revealed a second order oxidative addition rate constant approximately 500-600 times faster than that observed for the Monsanto catalyst [Rh(CO)₂I₂]⁻. The reaction rate of the first oxidative addition step in chloroform was not influenced by the increasing alkyl chain length of the R group on the β-diketonato ligand: k₁ = 0.0333 ([Rh((C₆H₅)COCHCO(CH₂CH₃))(CO)(PPh₃)]), 0.0437 ([Rh((C₆H₅)COCHCO(CH₂CH₂CH₃))(CO)(PPh₃)]) and 0.0354 dm³ mol⁻¹ s⁻¹ ([Rh((C₆H₅)COCHCO(CH₂CH₂CH₂CH₃))(CO)(PPh₃)]). The pK_a^′ and keto-enol equilibrium constant, K_c, of the β-diketones (C₆H₅)COCH₂COR, along with apparent group electronegativities, χ_R of the R group of the β-diketones (C₆H₅)COCH₂COR, give a measurement of the electron donating character of the coordinating β-diketonato ligand: (R, pK_a^′, K_c, χ_R) = (CH₃, 8.70, 12.1, 2.34), (CH₂CH₃, 9.33, 8.2, 2.31), (CH₂CH₂CH₃, 9.23, 11.5, 2.41) and (CH₂CH₂CH₂CH₃, 9.33, 11.6, 2.22).     

Synthesis and structural characterisation of rhodium hydride complexes bearing N-heterocyclic carbene ligands

Addition of excesses of N-heterocyclic carbenes (NHCs) IEt₂Me₂, IⁱPr₂Me₂ or ICy (IEt₂Me₂ = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene; IⁱPr₂Me₂ = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene; ICy = 1,3-dicyclohexylimidazol-2-ylidene) to [HRh(PPh₃)₄] (1) affords an isomeric mixture of [HRh(NHC)(PPh₃)₂] (NHC = IEt₂Me₂ (cis-/trans-2), IⁱPr₂Me₂ (cis-/trans-3), ICy (cis-/trans-4) and [HRh(NHC)₂(PPh₃)] (IEt₂Me₂(cis-/trans-5), IⁱPr₂Me₂ (cis-/trans-6), ICy (cis-/trans-7)). Thermolysis of 1 with the aryl substituted NHC, 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene (IMesH₂), affords the bridging hydrido phosphido dimer, [{(PPh₃)₂Rh}₂(μ-H)(μ-PPh₂)] (8), which is also the reaction product formed in the absence of carbene. When the rhodium precursor was changed from 1 to [HRh(CO)(PPh₃)₃] (9) and treated with either IMes (=1,3-dimesitylimidazol-2-ylidene) or ICy, the bis-NHC complexes trans-[HRh(CO)(IMes)₂] (10) and trans-[HRh(CO)(ICy)₂] (11) were formed. In contrast, the reaction of 9 with IⁱPr₂Me₂ gave [HRh(CO)(IⁱPr₂Me₂)₂] (cis-/trans-12) and the unusual unsymmetrical dimer, [(PPh₃)₂Rh(μ-CO)₂Rh(IⁱPr₂Me₂)₂] (13). The complexes trans-3, 8, 10 and 13 have been structurally characterised.     

Mononuclear ruthenium complexes containing two different phosphines in trans position: II. Catalytic hydrogenation of CC and CO bonds

Bis(acetate) ruthenium(II) complexes of the general formula Ru(CO)₂(OAc)₂(PⁿBu₃)[P(p-XC₆H₄)₃] (OAc = acetate, X = CH₃O, CH₃, H, F or Cl), containing different phosphine ligands trans to PⁿBu₃, have been employed as catalyst precursors for the hydrogenation of 1-hexene, acetophenone, 2-butanone and benzylideneacetone. For comparative purposes, analogous reactions have been performed using the homodiphosphine precursors Ru(CO)₂(OAc)₂(PⁿBu₃)₂ and Ru(CO)₂(OAc)₂(PPh₃)₂. The catalytic activity of the heterodiphosphine complexes depends on the basicity of the triarylphosphine trans to PⁿBu₃ as this factor controls, inter alia, the rate of formation of hydride(acetate), Ru(CO)₂(H)(OAc)(PⁿBu₃)[P(p-XC₆H₄)₃], or dihydride, Ru(CO)₂(H)₂(PⁿBu₃)[(p-XC₆H₄)₃], complexes, by hydrogenation of the bis(OAc) precursors. The catalytic hydrogenation of the CC double bond is best accomplished by homodiphosphine dihydride catalysts, while heterodiphosphine monohydrides are more efficient catalysts than the homo- and heterodiphosphine dihydrides for the reduction of the keto CO bond.     

Zr1−xLnxW2O8−x/2 (Ln=Eu, Er, Yb): Solid solutions of negative thermal expansion-synthesis, characterization and limited solid solubility

Zr_1−xLn_xW₂O_8−x/2 solid solutions (Ln=Eu, Er, Yb) of different substitution fractions x have been synthesized. Their X-ray diffraction (XRD) patterns have been indexed and lattice parameters calculated based on the α-ZrW₂O₈ structure. The coefficients of thermal expansion (CTEs) of these solid solutions were estimated to be −10.3×10⁻⁶ K⁻¹ in temperature range of 30-100 °C. The solubility of lanthanide ions in these solid solutions decreases linearly with the increase in the radius of substituted lanthanide ions. Based on the concentration dependence of phase transition temperatures, a novel method for determination of solubility of the lanthanide ions in Zr_1−xLn_xW₂O_8−x/2 solid solutions has been developed. This method seems to be more sensitive as compared with that based on XRD technique.     

Synthesis and characterization of new Rh complexes bearing CO, PPh3 and chelating P,O- or Se,Se-ligands: Application to hydroformylation of styrene

The complexes [Rh(CO)(PPh₃){Ph₂PNP(O)Ph₂-P,O}] (3), [Rh(CO)₂{Ph₂P(Se)NP(Se)Ph₂-Se,Se′}] (5), and [Rh(CO)(PPh₃){Ph₂P(Se)NP(Se)Ph₂-Se,Se′}] (6), were synthesised by stepwise reactions of CO and PPh₃ with [Rh(cod){Ph₂PNP(O)Ph₂-P,O}] (2) and [Rh(cod){Ph₂P(Se)NP(Se)Ph₂-Se,Se′}] (4), respectively. The complexes 3, 5 and 6 have been studied by IR, as well as ¹H and ³¹P NMR spectroscopy. The ν(CO) bands of complexes 3 and 6 appear at approximately 1960 cm⁻¹, indicating high electron density at the Rh^I centre. The structure of complexes 3 and 6 has been determined by X-ray crystallography, and the ³¹P NMR chemical shifts have been resolved via low temperature NMR experiments. Both complexes exhibit square planar geometry around the metal centre, with the five-membered ring of complex 3 being almost planar, and the six-membered ring of complex 6 adopting a slightly distorted boat conformation. The C-O bond of the carbonyl ligand is relatively weak in both complexes, due to strong π-back donation from the electron rich Rh^I centre. The catalytic activity of the complexes 2, 3 and 6 in the hydroformylation of styrene has been investigated. Complexes 2 and 3 showed satisfactory catalytic properties, whereas complex 6 had effectively no catalytic activity.     

First examples of [Rh(Bident)(CO)(L)] complexes where L is N-donor ligand: Molecular structure of [Rh(8-Oxiquinolinato)(CO)(NH3)]

Selective oxidation of one (trans to N) carbonyl group in [Rh(8-Oxiquinolinato)(CO)₂] with stoichiometric amount of Me₃NO in MeCN produces a solution containing [Rh(Oxq)(CO)(Me₃N)] and [Rh(Oxq)(CO)(MeCN)]. The ammonia complex, [Rh(Oxq)(CO)(NH₃)], has been prepared by action of NH₃ gas on this solution and characterized by IR, ¹H and ¹³C NMR, and X-ray data. Spectral parameters, ν(CO), δ¹³C, and ¹J(CRh), were measured in situ for a series of complexes [Rh(Oxq)(CO)(L)] (L = NAlk₃, Py, PBu₃, PPh₃, P(OPh)₃, C₈H₁₄) formed upon action of L on [Rh(Oxq)(CO)(NH₃)] in THF. A new ν(CO) and δ¹³C based scale of σ-donor/π-acceptor properties of ligands L is proposed including NH₃ and CO as the natural endpoints.     

Synthesis and characterization of La2Mo2O9 obtained from freeze-dried precursors

La₂Mo₂O₉ ceramics have been prepared from freeze-dried precursors and their properties compared to those of lantanum molybdate obtained by conventional solid state (SS) reaction. All materials have been characterized by X-ray diffraction, scanning electron microscopy and thermal analysis (TGA/DTA/DSC and dilatometry) to characterize the phase formation and phase transition. When the freeze-dried method was applied, the synthesis temperature required to obtain dense samples was much lower than that for powders obtained by SS reaction. The morphology and structure of the oxide particle are significantly dependent on the synthesis method. The grain size is smaller, whereas the density of sintered pellets is higher for the freeze-dried precursor powder when compared with the SS reaction method. Impedance spectroscopy was used to measure the electrical conductivity of La₂Mo₂O₉ from 548 to 1123 K, in air, and to characterize the blocking effects of grain boundaries.     

Structure and thermal decomposition of sulfated β-cyclodextrin intercalated in a layered double hydroxide

The sodium salt of hexasulfated β-cyclodextrin has been synthesized and intercalated into a magnesium-aluminum layered double hydroxide by ion exchange. The structure, composition and thermal decomposition behavior of the intercalated material have been studied by variable temperature X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma emission spectroscopy (ICP), and thermal analysis (TG-DTA) and a model for the structure has been proposed. The thermal stability of the intercalated sulfated β-cyclodextrin is significantly enhanced compared with the pure form before intercalation.     

Cyclorhenated compounds derived from 1,4-diaryl-1-azabutadienes: preparation, structures and reactions

PhCH₂Re(CO)₅ reacted with 1,4-diaryl-1-azabutadienes to give cyclometallated (η²-(C,N)-azabutadiene)Re(CO)₄ (4) together with the substituted derivatives (η¹-(N)-azabutadiene)(η²-(C,N)-azabutadiene)Re(CO)₃ (6 and 7) The substituted product was shown by NMR and X-ray crystal structure analysis to be an inseparable mixture of isomers differing in the conformation of the η¹-ligand about the NC bond—trans for (6) and cis for (7). Reaction of the mixture of 6 and 7 from 1,4-diphenyl-1-azabutadiene with phenyl acetylene gave η⁵-(1,2,4-triphenyl-1-aza-cyclohexadienyl)Re(CO)₃.     

Chemoselective hydrogenation of α,β-unsaturated ketones to allylic alcohols, catalyzed by a mononuclear ruthenium complex containing trans PBu3 and PPh3 ligands

The ruthenium(II) bis(acetate) complex Ru(CO)₂(OAc)₂(PⁿBu₃)(PPh₃) (OAc = acetate) containing two different trans phosphine ligands, has been employed as pre-catalyst for the chemoselective hydrogenation of α,β-unsaturated ketones to allylic alcohols. Analogous catalytic reactions with the homodiphosphine pre-catalysts Ru(CO)₂(OAc)₂(PⁿBu₃)₂ and Ru(CO)₂(OAc)₂(PPh₃)₂ gave lower conversions and selectivities. Batch catalytic reactions and operando high-pressure NMR experiments have contributed to establish that the hydrogenation of the CO group is performed by the heterodiphosphine monohydride RuH(CO)₂(OAc)(PⁿBu₃)(PPh₃) generated in situ by hydrogenation of the bis(OAc) precursor. PPh₃ unfastening from this monohydride complex is an essential condition for the occurrence of catalytic activity.     

Electrostatic forces that determine O,O-trans versus O,S-cis conformers in the aminated porphyrin complexes of Cd(N-NHCO-2-C4H3O-tpp)(OAc) and Cd(N-NHCO-2-C4H3S-tpp)(OAc)

Two new diamagnetic, mononuclear and aminated porphyrin complexes of O,O-trans-Cd (3-trans) and O,S-cis-Cd (4-cis) have been synthesized and characterized by ¹H, ¹³C NMR spectroscopy. The crystal structures of (acetato)(N-2-furancarboxamido-meso-tetraphenylporphyrinato)cadmium(II) [Cd(N-NHCO-2-C₄H₃O-tpp)(OAc); 3-trans] and (acetato)(N-2-thiophenecarboxamido-meso-tetraphenylporphyrinato)cadmium(II) [Cd(N-NHCO-2-C₄H₃S-tpp)(OAc); 4-cis] were determined. The coordination sphere around Cd²⁺ is a distorted square-based pyramid in which the apical site is occupied by a bidentate chelating OAc⁻ group for 3-trans and 4-cis. The plane of three pyrrole nitrogen atoms [i.e., N(1), N(2), N(4) for 3-trans and N(1), N(2), N(3) for 4-cis] strongly bonded to Cd²⁺ is adopted as a reference plane 3N. The N(3) and N(4) pyrrole rings bearing the 2-furancarboxamido (Fr) and 2-thiophenecarboxamido groups in 3-trans and 4-cis, respectively, deviate mostly from the 3N plane, thus orienting separately with a dihedral angle of 33.4° and of 31.0°. In 3-trans, Cd²⁺ and N(5) are located on different sides at 1.06 and −1.49 Å from its 3N plane, while in 4-cis, Cd²⁺ and N(5) are also located on different sides at 1.04 and −1.53 Å from its 3N plane. An attractive electrostatic interaction between the Cd²⁺ and O(4)⁻ atoms in furan stabilizes the O,O-trans conformer of 3. A repulsive electrostatic interaction between Cd²⁺ and S(1)⁺ destabilizes the O,S-trans conformer of 4. Both of these repulsive and the mutually attractive interactions between S(1)⁺ and O(3)⁻ atoms favor the O,S-cis rotamer of 4 both in the vapor phase and in low polarity solvents. NOE difference spectroscopy, HMQC and HMBC were employed for the unambiguous assignment of the ¹H and ¹³C NMR resonances of 3-trans and 4-cis in CDCl₃ at 20 and −50 °C.     

Synthesis of layered cathode material Li[CoxMn1−x]O2 from layered double hydroxides precursors

Cathode materials Li[Co_xMn_1−x]O₂ for lithium secondary batteries have been prepared by a new route—precursor method of layered double hydroxides (LDHs). In situ high-temperature X-ray diffraction (HT-XRD) and thermogravimetric analysis coupled with mass spectrometry (TG-MS) were used to monitor the structural transformation during the reaction of CoMn LDHs and LiOH·H₂O: firstly the layered structure of LDHs transformed to an intermediate phase with spinel structure; then the distortion of the structure occurred with the intercalation of Li⁺ into the lattice, resulting in the formation of layered Li[Co_xMn_1−x]O₂ with α-NaFeO₂ structure. Extended X-ray absorption fine structure (EXAFS) data showed that the Co-O bonding length and the coordination number of Co were close to those of Mn in Li[Co_xMn_1−x]O₂, which indicates that the local environments of the transitional metals are rather similar. X-ray photoelectron spectroscopy (XPS) was used to measure the oxidation state of Co and Mn. The influences of Co/Mn ratio on both the structure and electrochemical property of Li[Co_xMn_1−x]O₂ have been investigated by XRD and electrochemical tests. It has been found that the products synthesized by the precursor method demonstrated a rather stable cycling behavior, with a reversible capacity of 122.5 mAh g⁻¹ for the layered material Li[Co_0.80Mn_0.20]O₂.     

Synthesis and characterization of a tetraruthenium butterfly cluster containing a quadruply-bridging ligand derived from an N,N′-dipyrid-2-ylurea

The tetraruthenium cluster complex [Ru₄(μ₄-κ⁴-dmpu)(CO)₁₀], H₂dmpu = N,N′-bis(6-methylpyrid-2-yl)urea, has been prepared by treating [Ru₃(CO)₁₂] with H₂dmpu in toluene at reflux temperature. An X-ray diffraction study has determined that this cluster has a butterfly metallic skeleton hold up by a doubly-deprotonated N,N′-bis(6-methylpyrid-2-yl)urea ligand (dmpu). This ligand has the pyridine N atoms attached to the wing-tip Ru atoms and the amido N atoms spanning Ru-Ru wing-edges, in such a way that the cluster has C₂ symmetry. The donor atoms of doubly-deprotonated N,N′-dipyrid-2-ylureas seem to be appropriately arranged to hold butterfly tetranuclear clusters.     

RuO4-catalyzed oxidative polycyclization of the Cs-symmetric isoprenoid polyene digeranyl. An unexpected stereochemical outcome

The RuO₄-catalyzed oxidative polycyclization of digeranyl, a C_s-symmetric tetraene possessing a repetitive 1,5-diene structural motif, has been studied. The required substrate has been synthesized by Ti(III)-mediated tail-to-tail homocoupling of geranyl bromide. The process afforded two hitherto unknown isomeric tris-tetrahydrofuran products possessing unexpected all-threo cis-trans-cis and cis-trans-trans relative configuration. The new stereochemical outcome is explained based on previously formulated chelation or steric control models on the basis of structural differences between digeranyl and previously studied isoprenoid polyenes farnesyl acetate, geranylgeranyl acetate and squalene.     

Metallacyclic complexes with ortho-silylated triphenylphosphine ligands, LnOs(κ(Si,P)-SiMe2C6H4PPh2), derived from thermal reactions of the coordinatively unsaturated trimethylsilyl, methyl complex, Os(SiMe3)(Me)(CO)(PPh3)2

Reaction between Os(SiCl₃)Cl(CO)(PPh₃)₂ and five equivalents of MeLi produces a colourless intermediate, tentatively formulated as the lithium salt of the six-coordinate, dimethyl, trimethylsilyl-containing complex anion, Li[Os(SiMe₃)(Me)₂(CO)(PPh₃)₂]. Reaction of this material with ethanol releases methane and gives the red, coordinatively unsaturated methyl, trimethylsilyl-containing complex, Os(SiMe₃)(Me)(CO)(PPh₃)₂ (1). An alternative synthesis of 1 is to add one equivalent of MeLi to Os(SiMe₃)Cl(CO)(PPh₃)₂, which in turn is obtained by adding three equivalents of MeLi to Os(SiCl₃)Cl(CO)(PPh₃)₂. Treatment of 1 with p-tolyl lithium, again gives a colourless intermediate which may be Li[Os(SiMe₃)(Me)(p-tolyl)(CO)(PPh₃)₂], and reaction with ethanol gives the red complex, Os(SiMe₃)(p-tolyl)(CO)(PPh₃)₂ (3). Complexes 1 and 3 are readily carbonylated to Os(SiMe₃)(Me)(CO)₂(PPh₃)₂ (2) and Os(SiMe₃)(p-tolyl)(CO)₂(PPh₃)₂ (4), respectively. Heating Os(SiMe₃)Cl(CO)(PPh₃)₂ in molten triphenylphosphine results only in loss of the trimethylsilyl ligand and formation of the previously known complex containing an ortho-metallated triphenylphosphine ligand, Os(κ²(C,P)-C₆H₄PPh₂)Cl(CO)(PPh₃)₂. In contrast, heating the five-coordinate osmium-methyl complex, Os(SiMe₃)(Me)(CO)(PPh₃)₂ (1), in the presence of triphenylphosphine results mainly, not in tetramethylsilane elimination, but in ortho-silylation as well as ortho-metallation of different triphenylphosphine ligands giving, Os(κ²(Si,P)-SiMe₂C₆H₄PPh₂)(κ²(C,P)-C₆H₄PPh₂)(CO)(PPh₃) (5). A byproduct of this reaction is the non-silicon containing di-ortho-metallated complex, Os(κ²(C,P)-C₆H₄PPh₂)₂(CO)(PPh₃) (6). A similar reaction occurs when Os(SiMe₃)(Me)(CO)(PPh₃)₂ (1) is heated in the presence of tri(N-pyrrolyl)phosphine producing Os(κ²(Si,P)-SiMe₂C₆H₄PPh₂)(κ²(C,P)-C₆H₄PPh₂)(CO)[P(NC₄H₄)₃] (7) but a better synthesis of 7 is to treat 5 directly with tri(N-pyrrolyl)phosphine. Heating the six-coordinate complex, Os(SiMe₃)(Me)(CO)₂(PPh₃)₂ (2), gives two complexes both containing ortho-metallated triphenylphosphine, one with loss of the trimethylsilyl ligand, giving the known complex, Os(κ²(C,P)-C₆H₄PPh₂)H(CO)₂(PPh₃), and the other with retention of the trimethylsilyl ligand, giving Os(SiMe₃)(κ²(C,P)-C₆H₄PPh₂)(CO)₂(PPh₃) (8). Crystal structure determinations for 5, 6, 7 and 8 have been obtained.     

Imidazole-based bifunctional chelates for the “fac-[Re(CO)3]” core

Three monocationic rhenium(I) complexes of the type [Re(CO)₃(L)]Br, containing the bis-imidazole tridentate ligands bis-(2-(1-methylimidazolyl)methyl)amine (L¹), bis-(2-(1-methylimidazolyl)methyl)aminoethanol (L²) and bis-(2-(benzimidazolyl)ethyl)sulfide (L³), were prepared and characterized by ¹H NMR and IR spectroscopy. The complex salt [Re(CO)₃(L²)]Br (2) was also characterized by X-ray crystallography. The structure consists of discrete monocationic monomers with a fac-[Re(CO)₃]⁺ coordination unit, and the remaining three sites are occupied by one amine and two imidazolyl nitrogen donor atoms.     

Intercalation behavior of n-alkylamines into an A-site defective layered perovskite H2W2O7

Intercalation behavior of n-alkylamines into a protonated form of an A-site defective layered perovskite H₂W₂O₇ has been investigated. Results from XRD indicate these materials are layered with the corresponding interlayer spacing governed by the n-alkylamine chain length, and a reversible intercalation and deintercalation property is observed among these intercalation compounds. The IR spectra of the intercalation compounds with n-alkylamines clearly show that n-alkyl chains possess an all-trans conformation, and H₂W₂O₇ accommodate n-alkylamines (C_nH_2n+1NH₂: n=3, 4, 7, 8, 12, 16) to form intercalation compounds via an acid-base mechanism. A linear relationship between the interlayer distance and the number of carbon atoms in n-alkyl chains is observed to show a bilayer arrangement of the n-alkyl chains with a tilt angle of ∼71.6°. Elemental analysis studies reveal that the amounts of intercalated n-alkylamines are about 2.0 mol per [W₂O₇]. Despite the surface geometry of H₂W₂O₇ is almost identical to those of layered perovskites H₂[A_n−1B_nO_3n+1], the amounts of intercalated n-alkylamines of them are different. A reasonable explanation is given through our research.     

Metallacyclic complexes with ortho-stannylated triphenylphosphine ligands, LnOs(κ(Sn,P)-SnMe2C6H4PPh2), derived from thermal reactions of the five-coordinate complex, Os(SnMe3)Cl(CO)(PPh3)2

Heating the five-coordinate trimethylstannyl complex, Os(SnMe₃)Cl(CO)(PPh₃)₂, in solution with triphenylphosphine induces an ortho-stannylation of one phenyl group of a triphenylphosphine ligand and an ortho-metallation of another triphenylphosphine ligand, to produce the metallacyclic complexes, Os(κ²(Sn,P)-SnMeClC₆H₄PPh₂)(κ²(C,P)-C₆H₄PPh₂)(CO)(PPh₃) (1) and Os(κ²(Sn,P)-SnMe₂C₆H₄PPh₂)(κ²(C,P)-C₆H₄PPh₂)(CO)(PPh₃) (2), suggesting the possible intermediacy of a complex with a coordinated stannylene ligand. Spectroscopic data indicate that only one diastereomer of 1 is formed and crystal structure determination of 1 reveals that this is the diastereomer with chloride directed towards the CO ligand. Complex 2 is converted to 1 through a redistribution reaction with SnMe₂Cl₂. Heating the six-coordinate trimethylstannyl complex, Os(SnMe₃)Cl(CO)₂(PPh₃)₂, in solution produces the osmium(II) methyl complex, Os(Me)(SnMe₂Cl)(CO)₂(PPh₃)₂ (3), through an exchange of methyl and chloride groups on the tin and osmium. In this rearrangement, the relative locations of the two CO ligands and the two PPh₃ ligands remains unchanged. However, when the six-coordinate trimethylstannyl complex, Os(SnMe₃)Cl(CO)₂(PPh₃)₂ is heated under CO, the same exchange reaction is observed but the mono-triphenylphosphine, tricarbonyl complex, Os(Me)(SnMe₂Cl)(CO)₃(PPh₃) (4), is produced and here the SnMe₂Cl ligand is located trans to the PPh₃ ligand. Crystal structure determinations for 1, 2, 3, and 4 have been obtained.