Synthesis and X-ray crystal structure of trans-[MoF(CCH2 tBu)(Ph2PCH2CH2PPh2)2][BF4], a paramagnetic alkylidynefluorocomplex

Treatment of the alkynylhydridocomplex [MoH₃(CC^tBu)(dppe)₂](dppePh₂PCH₂CH₂PPh₂) with [Et₂OH][BF₄] gives trans-[MoF(CCH₂^tBu)(dppe)₂], the first example of a stable paramagnetic alkylidyne complex, the X-ray structure of which is reported.     

Rapid binding and activation of small molecules by [MoH4(Ph2PCH2CH2PPh2)2] in the presence of HBF4 · OEt2. Crystal structure of the product obtained with phenylacetylene trans-[MoF(η2-PhCCH)(Ph2PCH2CH2PPh2)2]BF4

In the presence of HBF₄ · OEt₂, [MoH₄(Ph₂PCH₂CH₂PPh₂)₂] exhibits a remarkably rapid and diverse range of reactions with a variety of small molecules. The crystal structure of the product obtained in the presence of phenylacetylene, trans-[MoF(η²-PhCCH)(Ph₂PCH₂CH₂PPh₂)₂]BF₄ is reported.     

Synthesis and crystal structure of [MoH3(CCBut)(Ph2PCH2CH2PPh2)2], a trihydrido-alkynyl complex

Reaction of Bu^tCCH with trans-[Mo(N₂)₂(dppe)₂] (dppe = Ph₂PCH₂CH₂PPh₂) gives [MoH₃(CCBu^t)(dppe)₂], whose X-ray structure is reported.     

Ligand-centred coupling of the alkynyl radical cations [Mo(CCR)(Ph2PCH2CH2PPh2)(η-C7H7)]+ (R = Ph or Bun: crystal structure of the dimeric product [Mo2(Ph2PCH2CH2PPh2)2(η-C7H7)2(μ-C4R2)][PF6]2 (R = Ph)

The radical cations [Mo(CCR)(dppe)(η-C₇H₇)]⁺ (R = Ph or Buⁿ); dppe = Ph₂PCH₂CH₂PPh₂) undergo coupling at C_β of the alkynyl ligand to afford the divinylidene-bridged, dimeric products [Mo₂(dppe)₂(η-C₇H₇)₂(μ-C₄R₂)]²⁺, characterised crystallographically for R = Ph.     

Heterobimetallic (RuCo) complexes with chelating and bridging Ph2PCH2PPh2 (dppm) ligands

Reaction of the heterobinuclear complex (CO)₄Ru(μ-PPh₂)Co(CO)₃ with Ph₂PCH₂PPh₂ (dppm) affords the dppm chelate (dppm)(CO)₂Ru(μ-PPh₂)Co(CO)₃ (1) and the dppm bridged molecule (CO)₃Ru(μ-PPh₂)(μ-dppm)Co(CO)₂ (2) both of which have been characterised by X-ray diffraction: 1 is the first binuclear RuCo complex containing a chelating dppm ligand and 2 the first heterobinuclear μ-dppm (RuCo) compound.     

Protonation of Cp(CO)(PPh3) RuCCPh: Formation of cationnic phenylacetylene and phenylvinylidene complexes and subsequent reaction with ethylene oxide to form the net [2 + 3] cycloadduct [Cp(CO)(PPH3)Ru=CCH(Ph)CH2CH2O]+

Protonation of the alkynyl complex Cp(CO)(PPh₃)RuCCPh (1) at low temperature affords quantitatively the vinylidened complex [Cp(CO)(PPh₃)RuCCH(Ph)]⁺ (3), which upon warming to room temperature forms an equilibrium with the η²-phenylacetylene complex [Cp(CO)(PPh₃)Ru(η²-HCCPh)]⁺ (4), with the latter predominating. Subsequent reaction with ethylene oxide yields the cyclic oxacarbene complex [Cp(CO)(PPH₃)Ru=CCH(Ph)CH₂CH₂O]⁺ (5), which can be regarded as the result of a net [3+2] cycloaddition reaction between 3 and ethylene oxide. Depronation of 5 affords teh corresponding neutral cyclic vinyl complex [Cp(CO)(PPH₃)RuC=C(Ph)CH₂CH₂O]⁺ (6), which can in turn be protonated to regenerate 5 in a diastereoselective manner. The structures of complexes 5 and 6 were determined by X-ray crystallography.     

The reversible adduct formation of group III trialkyls with relatively involatile phosphines; X-ray crystal structures of (Me3M)2·(Ph2PCH2)2 (M = Al,Ga, In) and (Me3Al)3·(Ph2PCH2CH2)2PPh

The following adducts of Group III trialkyls with phosphines have been prepared, either by direct reaction in hydrocarbon solution or by displacement of ether from the metal trialkyl etherate: Me₃M·PPh₃ (M = Ga, In); Me₃In·P(2-MeC₆H₄)₃; (R₃M)₂·(Ph₂PCH₂)₂ (R = Me, M = Al, Ga, In; R = Et, M = Ga, In; R = Buⁱ, M = Al); (Me₃M)₃·(Ph₂PCH₂CH₂)₂PPh (M = Al, Ga, In) and (Me₃M)₄·(Ph₂PCH₂CH₂PPhCH₂)₂ (M = Al, Ga, In). The compounds were analysed by ¹H and ³¹P NMR spectra of (Me₃M)₂·(Ph₂PCH₂)₂ (M = Ga, In) showed little change between 193 K and room temperature. Thermal dissociation of the adducts in vacuo gave the free metal trialkyl with no detectable contamination by the respective phosphine. Crystals of (Me₃M)₂·(Ph₂PCH₂)₂ (M = Al, Ga, In) are iso-structural and the molecules contain two distorted tetrahedral metals bridged by the (Ph₂PCH₂)₂; the MP distances are 2.544(4), 2.546(4) and 2.755(4) Å, respectively. The X-ray crystal structure of (Me₃Al)₃·(Ph₂PCH₂CH₂)₂PPh shows the molecule to contain distorted tetrahedral aluminium atoms bonded to each of the three phosphorus atoms, with AlP distances of 2.536(9) and 2.510(9) Å for the terminal and central moieties, respectively; the unit cell contains two such molecules plus one benzene molecule (the crystallizing solvent).     

The reaction of Sn[CH(SiMe3)2]2 with ethyne: formation of (HCC)Sn[CH(SiMe3)2]2(μ-trans-CHCH)Sn[CH-(SiMe3)2]2(CHCH2)

The reaction of Sn[CH(SiMe₃)₂]₂ and ethyne at ambient temperature affords a mixture of products, from which the title compound has been separated and identified by IR, ¹H, and ¹³C NMR spectroscopy.     

Crystal structure and fluxionality of the chiral cluster [HRu3(CCBut)(CO)7(dppm)] (dppm  Ph2PCH2PPh2). A novel racemization mechanism

The variable temperature ¹H, ¹³C and ³¹P NMR spectra of the complex [HRu₃(CCBu^t)(CO)₇(dppm)] (dppm  Ph₂PCH₂PPh₂), which crystallizes as an ordered racemic array of the two enantiomers, reveals a fluxional behaviour induced by the diphosphine, involving racemization via acetylide rotation and concurrent hydride migration.     

Synthesis of transition-metal Lewis acid adducts of trans-[ReCl(CNR)(Ph2PCH2CH2PPh2)2] (R = alkyl). A chemical and a quantum-chemical study of electrophilic β-addition to ligating isocyanide

Treatment of trans-[ReCl(CNR)(dppe)₂] (R = Me or Bu^t, dppe = Ph₂PCH₂CH₂ PPh₂) with CoCl₂(THF)_1.5, [ReOCl₃(PPh₃)₂] or [WCl₄L₂] (L = PPh₃ or PEtPh₂) affords the dinuclear adducts [ReCl(CN(M)R)(dppe)₂] (M = CoCl₂(THF), ReOCl₃(PPh₃) or WCl₄L, respectively) (formed via electrophilic β-addition of the electron-acceptor molecules to the isocyanide ligands), which undergo dissociation oxidation (for M = CoCl₂(THF) or ReOCl₃(PPh₃)). These reactions are considered in the light of results of extended Hückel calculations.     

Redox properties of the carbyne,aminocarbyne and η2-vinyl complexes trans-[ReCl(LH)(dppe)2][BF4] (LH  CCH2But,CCH2Ph,CNH2 or η2-C(CH2Ph)CH2) and of their parent vinylidene,isocyanide and allene compounds

The redox properties of the carbyne-, aminocarbyne- and η²-vinyl-(metallacyclopropene) complexes trans-[ReCl(LH)(dppe)₂][BF₄] (1; LH  CCH₂R (R Bu^t or Ph), CNH₂ and η²-C(CH₂Ph)CH₂; dppe  Ph₂PCH₂CH₂PPh₂), as well as of their parent vinylidene, isocyanide and allene complexes, trans-[ReClL(dppe)₂] (2; L  CCHR, CNH or

, have been studied by cyclic voltammetry and controlled potential electrolysis in aprotic media. The results are interpreted in terms of anodically- or cathodically-induced β-dehydrogenation processes of complexes (1), to give the corresponding compounds (2) (in the oxidized or the neutral form), as well as of a reversible dissociation of the former into the latter, in a basic solvent. The electrochemical P_L ligand parameter has been estimated for all these ligands.     

The reactions of phenylacetylene with naphthalene complexes of europium and ytterbium. Molecular structure of [IYbC≡CPh(DME)2]2

Reactions of naphthaleneeuropium and naphthaleneytterbium, C₁₀H₈Ln(DME) (Ln = Eu or Yb), with phenylacetylene are accompanied by the formation of the C-C bond and yield the complexes of composition Ph₂C₄H₂Ln(DME)₂. Hydrolysis of the Ph₂C₄H₂Ln(DME)₂ complexes affords a mixture of isomers of 1,4-diphenyl-1,3-butadiene. Reactions of C₁₀H₈[LnI(DME)₂]₂ with PhCCH yield mixed iodine-ethynyl complexes [ILn(-CCPh)(DME)₂]₂. According to the data of X-ray diffraction analysis, the ytterbium complex consists of two YbI(DME)₂ units bonded through two bridging CCPh groups. The crystals of this complex belong to the space groupP2₁/c. The central cyclic Yb-C-Yb-C fragment is planar; the C(I)-Yb(I)-C(I) angle is 86.4(3)°. The Yb-C bond lengths are 2.584(8) and 2.603(9) Å.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2101–2104, August, 1996.     

Preparation of cis-bis-acetylene-bis(pentafluorophenyl)-palladium(II) and -platinum(II) complexes,crystal structure of cis-[Pt(C6F5)2 (PhCCPh)2]

Treatment of cis-[M(C₆F₅)₂(THF)₂] (M = Pd, Pt; THF = tetrahydrofuran) with PhCCPh has given the novel bis-acetylene-palladium(II) and -platinum(II) complexes cis-[M(C₆F₅)₂(PhCCPh)₂]; these are stable even though there seems to be no significant π-back bonding according to the X-ray structure of the platinum complex.     

Heterobimetallic complexes of palladium(II) bridged by the mixed phosphine–phosphine oxide ligand Ph2PCH2CH2P(O)Ph2

The mixed phosphine–phosphine oxide Ph₂PCH₂CH₂P(O)Ph₂ (dppeO) reacts with either trans-[PdCl₂(PhCN)₂], Na₂[PdCl₄] or trans-[PdCl₂(DMSO)₂] to give trans-[PdCl₂{¹-Ph₂PCH₂CH₂P(O)Ph₂}₂]. Treatment of the latter with the metal chlorides, MCl₂ · nH₂O (M = Mn, Cu, Co, Zn, Hg; n = 4, 2, 6, 1, 0, respectively) or with Me₂SnCl₂ or SnCl₄ · 5H₂O, or with UO₂(NO₃)₂ · 6H₂O or UO₂(OAc)₂ · 2H₂O gives heterobimetallic complexes: trans-[PdCl₂{-Ph₂PCH₂CH₂P(O)Ph₂}₂MX₂] · nH₂O. The cobalt complex (MX₂ = CoCl₂) was unstable in solution (MeOH or EtOH/CHCl₃), and reverts to trans-[PdCl₂{¹-Ph₂PCH₂CH₂P(O)Ph₂}₂] and CoCl₂. trans-[PdCl₂{¹-Ph₂PCH₂CH₂P(O)Ph₂}₂] does not apparently react with either NiCl₂ · 6H₂O or CdCl₂ · 2.5H₂O.     

Formation and crystal structure of MeIr(CO)(PPh3)2(MeCO2CHCHCO2Me). Comparison of the structures of analogous alkene and alkyne complexes

The complex MeIr(CO)(PPh₃)₂(MeCO₂CHCHCO₂Me), synthesized from trans-MeIr(CO)(PPh₃)₂ and dimethyl maleate, crystallizes in the centrosymmetric monoclinic space group P2/n with a 13.997(5), b 17.878(5), c 15.709(4) Å, β 91.00(2)°, V 3930(2) ų and Z = 4. X-ray data (Mo-K_α, 2θ 4.5–45.0°) were collected with a Syntex P2₁ automated four-circle diffractometer; the structure was solved and converged with R 5.5% for all 5069 unique reflections and R 4.3% for those 4343 data with |F_o| > 3σ(|F_o|). The iridium(I) center has a distorted trigonal bipyramidal geometry with the Me and CO ligands occupying axial sites (Ir-Me(1) 2.159(8), IrCO 1.907(8) Å. The MeCO₂CHCHCO₂Me ligand is bonded in η² fashion to the iridium, with its coordinated double bond parallel to the equatorial plane. Bonds to the equatorial ligands are IrP(1) 2.344(2), Ir-P(2) 2.376(2) and Ir-(center of olefin) 2.017 Å. The observed ligand configuration is different from that for MeIr(CO)(PPh₃)₂(MeCO₂CCCO₂Me) which has axial Me and PPh₃ ligands in its thermodynamically stable isomer.     

(C60)2Ru2Cl4[Ph2P(CH2)4PPh2]配合物的合成

在氮气氛中采用配体取代法合成了C60以σ-π配位方式与Ru形成的稳定η2型富勒烯双核钌金属配合物(C60)2Ru2Cl4[Ph2P(CH2)4PPh2],其结构经UV,IR,XPS,XRD和元素分析表征.     

Crystal Structure, Nano-particle Morphology and Interaction with ATP of[NH3CH2CH(NH2)CH3]2[M(Ⅵ)O2(OC6H4O)2] (M=Mo0.6W0.4) and Its Activity to Promote DNA Cleavage

The title complex[NH3CH2CH(NH2)CH3]2[M(Ⅵ)O2(OC6H4O)2](M=Mo0.6W0.4)was synthesized via a simple solution-phase chemical route. The determination of single crystal X-ray diffraction revealed that the title compound is crystallized in a monoclinic system with P2(1)/n space group, a=1.0913(10) nm, b=1. 0442(10) nm,c=1.8842(19) nm, α=90°, β=96.530(17)°, γ=90°,Z=4, and V=2. 133(4) nm3. The mononuclear anionic unit [M(Ⅵ)O2(OC6H4O)2]2- displays chiral pseudo-octahedral [MO6] coordination geometry and is ges show that the title complex is comprised of nano-particles with diameters ranging from 20 to 50 nm. The NMR study shows the 1 H downfield chemical shifts of [NH3CHaHbCH(NH2)CH3] cations in the title complex when it is mixed with adenosine-triphosphate(ATP), and the chemical shift difference between Ha and Hb is increased greatly,and most of the catecholate ligands dissociate from the central metal atoms. The DNA cleavage activity experiment reveals that DNA cleavage promoted by the title complex is lower than that by Na2MoO4 which possesses antitumor property, but higher than that by Na2WO4.     

Fixation and reduction of molecular nitrogen by [WH4(PC2H5Ph2)4] and [WH4(PCH3Ph2)4] in a γ-radiation field

Hydride complexes of W(IV) with dpep (diphenylethylphosphine) and dpmp (diphenylmethylphosphine) were irradiated in thf+C₆H₁₂(11) solutions, saturated with N₂+H₂(13). Radiation yields of hydrazine, ammonia and amines were evaluated. The mechanism of reduction of molecular nitrogen is discussed.