Formation and structure of diruthenium complexes Ru2(CO)6−n (PPh3) n {μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} (n=1, 2)

Ruthenium carbonyl triphenylphosphine complexes Ru₂(CO)_6−n (PPh₃) _n {μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} (n=1, 2) were obtained by the reaction of complex Ru₂(CO)₆{μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} containing the ruthenacyclopentadiene moiety with PPh₃ in refluxing toluene. The complexes were characterized by IR and by¹H,¹³C, and³¹P NMR spectroscopy, and by X-ray analysis. The monophosphine derivative is identical to the complex formed by fragmentation of the Ru₃(CO)₈(PPh₃){μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} cluster and contains the PPh₃ ligand at the ruthenium atom of the ruthenacyclopentadiene moiety. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1836–1843, September, 1998     

Electrochemical study of heteronuclear complex [Cp(CO)2MnCu(μ-C=CHPh)(μ-Cl)]2

The electrochemical behavior of the heteronuclear dimeric vinylidene complex [Cp(CO)₂MnCu(μ-C=CHPh)(μ-Cl)]₂ (I) is studied using polarography, cyclic voltammetry, and controlled-potential electrolysis on mercury and platinum electrodes in acetonitrile. The dimer is reduced in two two-electron stages: at the first stage, metal-halogen bonds are broken and binuclear monomers [Cp(CO)₂MnCu(μ-C=CHPh)(Cl)]^? are formed; at the second stage, mononuclear manganese complexes Cp(CO)₂Mn=C=CHPh, metallic copper, and chloride ions are formed. The two-electron oxidation of dimer [Cp(CO)₂MnCu(μ-C=CHPh)(μ-Cl)]₂ also results in the formation of binuclear monomers, which decompose to complex Cp(CO)₂Mn=C=CHPh, Cu²⁺ ions, and Cl^? ions.     

[C5H4C(CH3)2CH2CH=CH2]Sm(OH)Cl·2MgCl2·4THF的晶体结构分析

用Ｘ－射线晶体结构衍射法测定了［Ｃ５Ｈ４Ｃ（ＣＨ３）２ＣＨ２ＣＨ＝ＣＨ２］Ｓｍ（ＯＨ）Ｃｌ·２ＭｇＣｌ２·４ＴＨＦ的晶体结构。它属三斜晶系,空间群为Ｐ＾－１,ａ＝１０．７７３（２）,ｂ＝１２．８３６（３）,ｃ＝１５．４７８（３）Ａ,ａ＝１１１．４６（３）,β＝１０７．７１（３）,γ＝９２．５４（３）°,Ｖ＝１８６８（１）Ａ＾３,Ｍｒ＝８２７．９１,Ｄｘ＝１．４７２ｇ／ｃｍ＾３,μ＝２．０００６ｍｍ     

Synthesis and characterisation of [RuCl2(PPh3)2(C16H11NO)] complex

The reaction of [RuCl₂(PPh₃)₃] complex with 1-isoquinolyl phenyl ketone has been examined. A new ruthenium(II) complexes–[RuCl₂(PPh₃)₂(C₁₆H₁₁NO)] has been obtained and characterised by IR and UV-VIS measurements. Crystal structure of the complex has been determined. The electronic spectrum of the complex has been calculated by TDDFT method.     

Theoretical investigation on mechanism for OH-initiated oxidation of CH2=C(CH3)CH2OH

The mechanism of the gas-phase reaction OH with CH₂=C(CH₃)CH₂OH (2-methyl-2-propen-1-ol) has been elucidated using high-level ab initio method, i.e., CCSD(T)/6-311++g(d,p)//MP2(full)/6-311++g(d,p). Various possible H-abstraction and addition–elimination pathways are identified. The calculations indicate that the addition–elimination mechanism dominates the OH+MPO221 reaction. The addition reactions between OH radicals and CH₂=C(CH₃)CH₂OH begin with the barrierless formation of a pre-reactive complex in the entrance channel, and subsequently the CH₂(OH)C(CH₃)CH₂OH (IM1) and the CH₂C(OH)(CH₃)CH₂OH (IM2) are formed by OH radicals’ electrophilic additions to the double bond. IM1 can easily rearrange to IM2 via a 1,2-OH migration. Subsequently, rearrangement of IM2 to form (CH₃)₂C(OH)CH₂O (IM11) followed by dissociation to HCHO + (CH₃)₂COH (P21) is the most favorable pathway. The decomposition of IM2 to CH₂OH + CH₂=C(OH)CH₃ (P16) is the secondary pathway. The other pathways are not expected to play any important role in forming final products.     

Monosubstituted Trinuclear and Tetranuclear VIB Metal Carbonyl Complexes: Syntheses of [{M(CO)5}3(Pf-Pf-Pf)] [Pf-Pf-Pf = PhP(CH2CH2PPh2)2] and [{M(CO)5}4(P-Pf3)] [P-Pf3 = P(CH2CH2PPh2)3] (M = Cr,Mo) and Crystal Structures of the Latter Three

The triligate trimetallic complexes, [{M(CO)₅}₃(Pf-Pf-Pf)] and tetraligate tetrametallic complexes, [{M(CO)₅}₄(P-Pf₃)] (M = Cr and Mo), were prepared from [M(CO) ₆] and the corresponding ligands in MeCN/CH₂Cl₂ promoted by Me₃NO at 0 °C. Crystals of trimer lb are monoclinic, space group P 2₁/n, with a = 13.407(3), b = 15.002(5), c = 26.52(1) Å, β = 90.65(2)°, Z = 4, and R = 0.060 for 2760 observed reflections. Crystals of tetramer 2a are monoclinic, space group P 2₁/c, with a – 14.183(8), b = 29.880(4), c = 16.103(2) Å, β = 94.98(3)°, Z = 4, and R = 0.039 for 5014 observed reflections. Crystals of 2b are monoclinic, space group C 2/c, with a = 42.120(8), b = 13.679(1), c = 23.486(2) Å, β = 92.14(1)°, Z = 8, and R = 0.032 for 6897 observed reflections. Each phosphorus atom of the ligands is coordinated to the M(CO)₅ moiety in each title compounds. The geometry of the four metals is a distorted tetrahedron for the tetramers.     

Osmabenzenes from the reactions of HC[triple bond]CCH(OH)C[triple bond]CH with OsX2(PPh3)3 (X = Cl, Br)

Treatment of OsX2(PPh3)3 (X = Cl, Br) with HCCCH(OH)CCH in THF produces OsX2(CH=C(PPh3)CH(OH)CCH)(PPh3)2, which reacts with PPh3 to give osmabenzenes [Os(CHC(PPh3)CHC(PPh3)CH)X2(PPh3)2]+.     

The seven‐membered nickelacycle [NiBr{o‐CH=C(CF3)C6H4CH2PPh2‐κ2C,P}{PPh(CH2Ph)2}]

The crystal and molecular structures of the title compound, 3‐bromo‐3‐(di­benzyl­phenyl­phospho­nio)‐2,2‐di­phenyl‐5‐trifluoromethyl‐1H‐benzo­[e][1,2]­phosphanickelepine, [NiBr(C₂₂H₁₇F₃P)(C₂₀H₁₉P)], which was obtained as the major regioisomer from insertion of HCCCF₃ into the Ni—C bond of the five‐membered phosphanickelacycle [NiBr(o‐C₆H₄CH₂PPh₂‐κ²C,P){PPh(CH₂Ph)₂}], have been determined. Principal geometric data include the Ni—X bond lengths Ni—Br 2.3343 (4) Å, Ni—P 2.1867 (7) and 2.2094 (7) Å, and Ni—C 1.882 (3) Å, and the two trans angles P—Ni—P 171.55 (3)° and Br—Ni—C 176.88 (9)°.     

Complex Formation of [Ph2P(O)I2 C=CH2 and [Ph2 P(O) I2 C=PPh3 with Phosphorus and Tantalum Pentafluorides

Abstract

Reactions of PF₅ and TaF₅ with [Ph₂P(O)]₂ C=CH₂ (I) and [Ph₂P(O)]₂ C=PPh₃ (II) in MeCN and CH₂Cl₂ were studied by means of ¹⁹F, ³¹P, ¹H and ¹³C NMR spectroscopy. It has become evident, that one or two phosphoryl groups in (I) and (II), as well as in cis- and trans-Ph₂P(O)CH=CHP(O)Ph₂, are involved in complex formation. The formation of tetra-fluoro cations PFL and PF₄L along with pentafluorocom-plexes PF₅L and TaF₅L was found. Ligands are coordinated with central ions of complexes as chelates. The trans-atoms F₁ of TaF ₅L are nonequivalent because of nonsymmetric position to the Ph3P-group. The F₁-atoms in PF₄L are supposed to be symmetric to the Ph₃P-group. The formation of tri-fluorocomplexes TaOF₃L was also observed. Since the position of ¹⁹F NMR resonance lines of TaOF₃L is near to that of pentafluorocomplexes, it can be supposed that either the change of Ta coordination number takes place, either oxygen atom comes into complex with inner sphere in the reaction with ligand or during hydrolysis.     

Ab initio studies on reaction H2C=C(OH)Li+CH3 + (CH3 -)

The possible structures and isomerizations of H₂C=C(OH)Li are studied theoretically by the gradient analytical method at RHF/6-31+G level. According to these results, reactions of H₂C=C(OH)Li with CH₃ ⁺ and CH ₃ ^- are investigated thoroughly. When H₂C=C(OH)Li reacts with CH ₃ ⁺ , H_zC=C(OH)Li firstly changes from structure1 to structure4, and then combines with CH₃ ⁺. In this reaction, the configuration of central carbon is retained. When H₂C=C(OH)Li reacts with CH ₃ ^- , structure1 firstly breaks its C-O bond to give contact ion-pair. Then through transition state16 which is similar to structure2, the attack of CH ₃ ^- from the opposite side of^-OH replaces^-OH group and inverts the configuration of carbenoid carbon atom. All the results show that the ambident reactivity of carbenoid has close relationship with the stability of special structures. Project supported by the National Natural Science Foundation of China (Grant No. 29773025).     

(PPh4)2[OsCl3(NO)(SnCl3)2] Synthese,IR-Spektrum und Kristallstruktur

(PPh₄)₂[OsCl₃(NO) (SnCl₃)₂]; Preparation, I.R. Spectrum, and Crystal Structure (P(C₆H₅)₄)₂[OsCl₃(NO)(SnCl₃)₂] yields from the reaction of OsCl₃(NO) with PPh₄-[SnCl₃] in dichloro methane forming red crystals. The complex crystallizes monoclinic in the space group C2/c with four formula units per unit cell. The crystal structure was determined by aid of X-ray diffraction data (2261 independent, observed reflexions, R = 4.9%). The cell parameters are a = 1369, b = 1989, c = 2088 pm, β = 99.54°. The structure consists of tetraphenyl phosphonium cations and [OsCl₃(NO)(SnCl₃)₂]^2?-anions. In the anion the osmium is coordinated octahedrally by three chlorine atoms (mean bond length r Os? Cl 238 pm), two SnCl₃ groups in transposition to each other (r Os? Sn 265 pm) and the N-atom of the covalently bonded nitrosyl ligand (r Os? N 173 pm). The i.r. spectrum of the anion is reported and assigned.     

〔C_5H_4C(CH_3)_2CH_2CH=CH_2〕Sm(OH)Cl·2MgCl_2·4THF的晶体结构分析

用Ｘ－射线晶体结构衍射法测定了〔Ｃ５Ｈ４Ｃ（ＣＨ３）２ＣＨ２ＣＨ＝ＣＨ２〕Ｓｍ（ＯＨ）Ｃｌ·２ＭｇＣｌ２·４ＴＨＦ的晶体结构。它属三斜晶系,空间群为Ｐ１,ａ＝１０．７７３（２）,ｂ＝１２．８３６（３）,ｃ＝１５．４７８（３）,α＝１１１．４６（３）,β＝１０７．７１（３）,γ＝９２．５４（３）°,Ｖ＝１８６８（１）３,Ｍｒ＝８２７．９１,Ｄｘ＝１．４７２ｇ／ｃｍ３,μ＝２．０００６ｍｍ－１,Ｆ（０００）＝８４０,Ｚ＝２,Ｒ＝０．０４１,ｗＲ＝０．０５０（Ｉ≥３σ（Ｉ））。分子中Ｓｍ原子的配位数为８,形成一个严重扭曲的八面体结构;２个Ｍｇ原子的配位情况相似,它们的配位数都是６,分别构成２个扭曲的八面体。这３个八面体通过３个共平面联接     

二(三苯基膦)水杨酸铜(Ⅰ)乙醇溶剂配合物的晶体结构

The crystal and molecular structure of [ (PPh3)2Cu(O2CPhOH)] @ CH3CH2OH has been determined by X-raycrystallography. It crystallizes in the monoclinic system, space group P21/c, with Mr = 771.26 (C45H41CuO4P2),a = 0. 96413(19) nm, b= 1. 5780(3) nm, c = 2. 5426(5) nm, β = 100. 27(3)°, V= 3. 8065(13) nm3, The titlecompound consists of discrete copper (Ⅰ) bis(triphenylphosphine) salicylate molecules and ethanol solvate. EachCu is coordinated to two phosphorus atoms of triphenylphosphine ligands and one of carboxylate oxygens in a trigonalplanar geometry. In the solid, the intramolecular hydrogen bond and extensive intermolecular interaction connecting(PPh3) 2Cu(O2CPhOH) molecules and ethanol solvate form hydrogen bonds network which stabilize the crystalstructure.     

A Novel Alkene(alkyl)(aqua)(aryl)platinum(II) Complex – [Pt{CH(CH2C6F5)CH2CH2CH=CH2}(C6F5)(OH2)]

From the reaction of PtCl₂(hex) (hex = hexa‐1,5‐diene) with LiC₆F₅ in diethyl ether, the complex [Pt{CH(CH₂C₆F₅)CH₂CH₂CH=CH₂}(C₆F₅)(OH₂)] ( 1 ) was isolated. The crystal structure (monoclinic, C2/c (no. 15), Z = 8, a = 15.241(3), b = 16.579(2), c = 16.225(2) Å, β = 111.12(2)°) shows a complex with square planar coordination around platinum with a template formed 1‐pentafluorophenylhex‐5‐en‐2‐yl ligand, and C₆F₅ and aqua ligands trans to the double bond and alkyl carbon, respectively.     

Reactivity of a rhodium(I) complex towards oxygen enhanced by a cyano ligand. Structure of [Rh(CN)(O2)(PPh3)2(XNC)] (XNC=xylyl isocyanide)

The complex [Rh(CN)(O₂)(PPh₃)₂(XNC)](CH₂Cl₂) has been obtained under ambient conditions from solutions containing trans-[Rh(CN)(PPh₃)₂(XNC)] upon exposure to air. The compound is unusual in that analogues containing the more strongly electron-donating ligands Cl⁻, N₃⁻ and NCO⁻ (among others) in place of CN⁻ are not formed.