The influence of the nature of the ligand,L, on the electrochemical behaviour of dinitrosyl molybdenum complexes,Mo(NO)2L2Cl2, in aprotic media

Electrochemical investigations of the reduction of dicationic, monocationic and neutral dinitrosyl molybdenum complexes in nitromethane and acetonitrile are reported. All the compounds with the general formulae: [Mo(NO)₂L₂L′₂]²⁺, [Mo(NO)₂L₂L′Cl]⁺ and Mo(NO)₂L₂Cl₂ (L = CH₃CN, CH₂CHCN, C₆H₅CN, C₅H₅N, P(C₆H₅)₃, L₂ = 2,2′-bipyridine, L′ = CH₃CN and L′₂ = 2,2′-bipyridine) are reducible by one electron to yield 19-electron complexes. The dicationic complexes undergo a reversible one-electron transfer. For the mono- and dichlorocomplexes, the one-electron transfer induces the facile exchange of the chloroligand in the 19-electron complexes except for L₂ = 2,2′-bipyridine. However, the exchange of the chloroligand is followed by the fast anation by Cl^? of the remaining 18-electron chlorocomplexes to afford [Mo(NO)₂Cl₃L]^? and [Mo(NO)₂Cl₄]^2? which are reducible at higher negative potentials than dichloro- and monochlorocomplexes. The multiple electrochemical step system is not catalytic, but of the electroactivation type.     

Mixed-metal single-molecule magnets: Syntheses, structure, and magnetic properties of [Mn8Fe4O12(O2CR)16(H2O)4] (R = CH2Cl, CH2Br, CHCl2)

Three mixed-metal single-molecule magnets containing [Mn₈Fe₄O₁₂]¹⁶⁺ cores are synthesized and characterized. The reaction of FeCl₂·4H₂O with KMnO₄ and RCOOH (R = CH₂Cl, CH₂Br) in H₂O gives [Mn₈Fe₄O₁₂(O₂CR)₁₆(H₂O)₄] (R = CH₂Cl (1), CH₂Br (2)) in yields of 43% and 40%, respectively. Treatment of complex 1 with an excess of CHCl₂COOH in CH₂Cl₂ gives [Mn₈Fe₄O₁₂(O₂CCHCl₂)₁₆(H₂O)₄]·CH₂Cl₂·10H₂O (3·CH₂Cl₂·10H₂O) in a yield of 83%. The X-ray structure analysis reveals that all three complexes consist of a trapped-valence dodecanuclear core comprising 4Mn^III, 4Fe^III, and 4Mn^IV ions. DC magnetic susceptibility and magnetization measurements indicate that all three complexes exhibit intramolecular antiferromagnetic interaction, resulting in an S = 4 ground state. In addition, frequency-dependent out-of-phase AC magnetic susceptibility signals at low temperature for complexes 1, 2, and 3 are indicative of their single-molecule magnetism behavior.     

Reductive elimination reaction of rhenium complexes trans-(η-C5Me5)Re(CO)2(chloroaryl)Cl

Thermal reaction of the chloroaryl-chloride complexes trans-(η⁵-C₅Me₅)Re(CO)₂(Ar^Cl)Cl (Ar^Cl = 3-ClC₆H₄, 3-ClC₆H₃(4-Me) and 3,5-Cl₂C₆H₃) in acetonitrile did not interconvert to the cis isomer, instead the complex ReCl(CO)₂(NCMe)₃ and the corresponding 5-Ar^Cl-1,2,3,4,5-pentamethylcyclopentadiene were formed. Similar reductive elimination products were obtained when the starting rhenium complexes were reacted with trimethylphosphite in toluene.     

Cluster compounds [Ca(DMF)6][Mo6Cl14] and [{Ca(OPPh3)4}{Mo6Cl14}]∞: Synthesis, crystal structure, and properties

The [Ca(DMF)₆][Mo₆Cl₁₄] complex (I) was synthesized by reacting octahedral cluster Mo complex (H₃O)₂Mo₆Cl₁₄·6H₂O with the Ca²⁺ cation in DMF. Analogous reaction carried out in the presence of triphenylphosphine oxide Ph₃PO in acetonitrile resulted in [{Ca(OPPh₃)₄}{Mo₆Cl₁₄}] (II). According to X-ray diffraction data, complex I has ionic structure, while the structure of complex II consists of infinite linear chains of the cluster anionic complexes {Mo₆Cl₁₄}²⁻ bonded to the cationic Ca complexes {Ca(OPPH₃)₄}²⁺. Both complexes exhibit intensive luminescence in red and near-IR regions of the spectrum. Original Russian Text ? Zh.S. Kozhomuratova, Yu.V. Mironov, M.A. Shestopalov, Ya.M. Gaifulin, N.V. Kurat’eva, E.M. Uskov, V.E. Fedorov, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 1, pp. 3–8.     

Catalytic oxidation of diorganotin(IV) carboxylates to mixed-ligand monoalkyltin(IV) carboxylates by Ag and structure characterization of the mixed-ligand monoalkyltin(IV) 2-pyridinecarboxylate (2-ClPhCH2)Sn(2-ClPhCO2)(O2CC5H4N-2)2

The complexes of the type (ArCH₂)₂SnO were catalytic-oxygenated by Ag⁺ and yielded mixed-ligand organotin(IV) complexes (ArCH₂)(2-C₅H₄NCO₂)₂(ArCOO)tin(IV) (Ar = C₆H₅ (1), 2-ClC₆H₄ (2), 2-CNC₆H₄ (3), 4-ClC₆H₄ (4), 4-CNC₆H₄ (5), 2-FC₆H₄ (6)). The complexes 1-6 are characterized by elemental analyses, IR and NMR (¹H, ¹³C, ¹¹⁹Sn) spectroscopies. Single X-ray crystal structure analysis has been determined, which reveals that the center tin atom of complex 2 is seven-coordinated geometry.     

35Cl Nqr spectroscopy of the [PO2Cl2]− and POCl3 groups in Me(PO2Cl2)2·2D (Me = Mg,Ca, Mn; D = POCl3,CH3COOC2H5,CH3COCH3)

³⁵Cl NQR spectra of dichlorophosphates Me(PO₂Cl₂)₂ · 2D (Me = Mg, Ca, Mn; D = CH₃COOC₂H₅, CH₃COCH₃, POCl₃) are studied in the temperature range 77 ? T (K) ? 305. It is shown that the three compounds with CH₃COOC₂H₅ as donor are isomorphic at 77 K, the crystal structure of Mn(PO₂Cl₂)₂· 2CH₃COOC₂H₅. The structure of Mg(PO₂Cl₂)_2^?· 2CH₃COCH₃ and of Mg(PO₂Cl₂)₂ · 2POCl₃ probably consists of infinite chains as found for Mn(PO₂Cl₂)₂· 2CH₃COOC₂H₅. Mg(PO₂Cl₂)₂· 2CH₃COOC₂H₅ shows phase transformations and a complicated dynamical behaviour leading to strong deviations from a Bayertype NQR function v = f(T). The donor capacity of POCl₃ in Mg(PO₂Cl₂)₂· 2POCl₃ is comparable with the donor strength in AsCl₃ · POCl₃ · A d_π-p_π overlap of the P-O bond influences the P-Cl bond.     

The evaluation of singlet-triplet separations for [W2(μ-H)(μ-Cl)Cl4(μ-dppm)2] and [W2(μ-H)2 (μ-O2CC6H5)2(P(C6H5)3)2] based on P NMR and crystallographic data

The singlet-triplet separations for the edge-sharing bioctahedral (ESBO) complex W₂(μ-H)(μ-Cl)(Cl₄(μ-dppm)₂ · (THF)₃ (II) has been studied by ³¹P NMR spectroscopy. The structural characterization of [W₂(μ-H)₂(μ-O₂CC₆H₅)₂Cl₂(P(C₆H₅)₃)₂] (I) by single-crystal X-ray crystallography has allowed the comparison of the energy of the HOMOLUMO separation determined using the Fenske-Hall method for a series of ESBO complexes with two hydride bridging atoms, two chloride bridging atoms and the mixed case with a chloride and hydride bridging atom. The complex representing the mixed case, [W₂(μ-H)(μ-Cl)Cl₄(μ-dppm)₂ · (THF)₃] (II), has been synthesized and the value of −2J determined from variable-temperature ³¹P NMR spectroscopy.     

An unusual oxidative addition-ligand elimination reaction. Preparation and structure of RhCl2(PMe2Ph)2(C3Ph3)

The sym-triphenylcyclopropenium cation (C₃Ph₃⁺) stabilized as the Cl^? or PF₆^? salt, undergoes facile reactions at room temperature with trans-Rh(CO)Cl(PMe₂Ph)₂ to produce complexes which result from the oxidative cleavage of the ring and decarbonylation of the organometallic reactant. The product of the C₃Ph₃⁺Cl^? reaction has been fully characterized by X-ray analysis and is shown to be RhCl₂(PMe₂Ph)₂(C₃Ph₃).     

[Bi2Cl10(H2-Norf)4(H2O)8](H-Norf是诺氟沙星)(英)

The crystal structure of [Bi2Cl10(H2-Norf)4(H2O)8] (1) comprises [H2-Norf]^ cations and [Bi2Cl10]4^- anions, that are loosely associated via H-bonding interactions, as well as water molecules that also participate in H-bonding interactions. Strong blue-fluorescent emission of 1 at solid state is observed at the room temperature. CCDC:238237.     

The electronic properties of isocyanides at rhenium—dinitrogen binding sites. Preparation and redox properties of the isocyanide complexes trans-[ReCl(CNR)(Ph2PCH2CH2PPh2)2]

The isocyanide complexes trans-[ReCl(CNR)(dppe)₂] (R  Me, Bu^t, C₆H₄CH₃-4, C₆H₄CH₃-2, C₆H₄Cl-4, C₆H₄OCH₃-4 and C₆H₃Cl₂-2,6; dppe  Ph₂PCH₂CH₂PPh₂) have been prepared by isocyanide displacement of dinitrogen from the parent complex trans-[ReCl(N₂)(ddpe)₂]. Their redox properties have been studied by cyclic voltammetry and are interpreted on the basis of the electronic properties and the geometry of the ligating isocyanides which are believed to be bent in these complexes, appearing to exhibit ligand parameter (P_L) values ca. +0.3 V higher than those which would be expected for linear geometry. A very high polarisability (B ? 3.4) is observed for the {ReCl(dppe)₂} site.     

A one-pot method to prepare the carbene complex [TpRhCl2(CHNiPr2)] from [TpRh(CO)2], CHCl3, and NHiPr2

The complex [Tp^Me₂,ClRh(CO)₂] reacts with chloroform to give quantitatively the rhodium(III) complex [Tp^Me₂,ClRhCl(CHCl₂)(CO)] resulting from the oxidative addition of a C-Cl bond. Further reaction with diisopropylamine gives the aminocarbene complex [Tp^Me₂,ClRhCl₂(CHNiPr₂)], whose X-ray crystal structure has been solved. Addition of an excess of diisopropylamine to [Tp^Me₂,ClRh(CO)₂] in chloroform provides directly [Tp^Me₂,ClRhCl₂(CHNiPr₂)].     

Supramolecular Systems Based on Ca2+, [Mo3O2S2Cl6(H2O)3]2s-, [Mo3S4Cl6.75Br0.25(H2O)2]3s- and Cucurbit[6]uril

Adducts of cucurbit[6]uril with Ca²⁺ and trinuclear cluster chloroaquacomplexes (H₉O₄)₂(H₇O₃)₂[(Ca(H₂O)₅)2(C₃₆H₃₆N₂₄O₁₂)]Cl₈·0.67H₂O (1) and [(Ca(H₂O)₅)₂(C₃₆H₃₆N₂₄O₁₂)]× [Mo₃O₂S₂Cl₆(H₂O)₃]₂·13H₂O (2) are obtained and structurally characterized. The structures of both compounds contain polymeric [Ca(H₂O) _n ]₂² CB[6]∞ cations that form infinite columns; the space between them is filled with Cl^s- (1) and [Mo₃O₂S₂Cl₆(H₂O)₃]^2s- (2). A new (H₇O₃)₂(H₅O₂)× [Mo₃S₄Cl_6.25Br_0.25(H₂O)₂](C₃₆H₃₆N₂₄O₁₂)·CH₂Cl₂·6H₂O complex (3) is also obtained and structurally characterized.     

Comparison of quantum, classical, and ring-polymer molecular dynamics infra-red spectra of Cl(H2O) and H(H2O)2

We present a comparison of the infra-red spectra of Cl⁻(H₂O) and H⁺(H₂O)₂ obtained with classical and ring-polymer molecular dynamics with previous quantum calculations. Full-dimensional ab initio-based potential and dipole-moment surfaces are used in these calculations.     

Formation of [CoCl4(H2O)2] complex in CoCl2·MgCl2·8H2O double salt: structural and energetic properties of [MCl4(H2O)2] and [M(H2O)6] (M=Mg, Co)

The crystal structure of the double salt CoCl₂·MgCl₂·8H₂O has been determined by the X-ray diffraction method. It crystallizes in the space group with a=6.0976(9), b=6.308(1), c=8.579(3) Å, α=81.99(2)°, β=88.40°, γ=84.61(1)°, Z=1, and R=0.027. The crystal consists of two kinds of well separated octahedra, [CoCl₄(H₂O)₂]²⁻ and [Mg(H₂O)₆]²⁺. The former is unique as aquachloro complexes of Co²⁺. In order to elucidate the reason prepared as such unique complexes in the double salts, formation energies for [MCl₄(H₂O)₂]²⁻ and [M(H₂O)₆]²⁺ (M=Co, Mg) have been calculated by using the density functional methods, and it has been revealed that the formation energies of the first coordination sphere for the metal ions and the Cl⁻?H₂O hydrogen bond networks around [CoCl₄(H₂O)₂]²⁻ play a decisive role in forming [CoCl₄(H₂O)₂]²⁻ with the regular octahedral geometry in the double salt.     

The polymerization of propadiene by Ni(acac)2, C3H4, RnAlX3−n catalysts

Catalyst formation in the system Ni(acac)₂, C₃H₄, R_nAlX_3?n was studied. Polymerization experiments showed that, by replacing ionic groups such as acac^?, Br^?, Cl^? with alkyl or hydride groups, an active catalyst is obtained. Electrolysis of Ni(acac)₂ in tetrahydrofuran also gives an active catalyst. Lewis acids like (iBu)₃Al and Et₃Al increase the polymerization rate, while Lewis bases like pyridine and triphenylphosphine not only decrease the rate but also change selectivity. The selectivity is not changed if different transition metals (e.g. Co, Pd, Ni) are used. Kinetic measurements show a first order dependence on Ni. The dependence on (iBu)₃Al changes from first to zero order with increasing $\text{Al}\text{Ni}$ ratio. This can be explained by assuming that the very active catalyst is formed via an equilibrium between a nickel complex and (iBu)₃Al. A first order deactivation of the nickel catalyst is observed; it is faster during polymerization than during ageing of the catalyst.     

纳米Ag@SiO2核壳结构的表面等离子体共振效应对铕配合物的荧光增强作用

分别制备了二氧化硅壳层厚度为10、25和80 nm的三种Ag@SiO₂纳米粒子, 合成了铕与不同比例苯甲酸根(BA)的配合物、铕与1, 10-邻菲罗啉(phen)及2, 2''-联吡啶(bpy)的配合物, 并对其进行表征. 表征结果推测配合物的组成为Eu(BA)_nCl_3-n·2H₂O (n=1, 2, 3)、Eu(phen)Cl₃·2H₂O和Eu(bpy)Cl₃·2H₂O. 配合物的荧光光谱显示, 在加入Ag@SiO₂纳米粒子后, 复合物的荧光强度有不同程度的增加, 这可能是由于表面等离子体共振造成的. 不同硅壳厚度的Ag@SiO₂纳米粒子的荧光增强顺序是25 nm>80 nm>10 nm, 这表明二氧化硅核壳厚度约25 nm时有较强的表面等离子体共振效应. 此外, 在这些复合物中, Eu(phen)Cl₃·2H₂O复合物的增强效果是最强的, 而Eu(BA)_nCl_3-n·2H₂O的增强效果是最弱的. 在三个苯甲酸铕配合物中, Eu(BA)₃·2H₂O的增强效果最弱, 其他两个苯甲酸铕复合物增强效果相对较好. 原因可能是含氮配合物(Eu(phen)Cl₃·2H₂O和Eu(bpy)Cl₃·2H₂O)可以和Ag@SiO₂更好地成键, 而苯甲酸铕配合物和Ag@SiO₂纳米粒子的作用相对较弱. Ag@SiO₂纳米粒子有望应用于增强稀土材料的发光.     

Demercuriation reactions of the complexes [(PPh3)2RPtHgR′] containing platinum-mercury bonds

The compounds [(PPh₃)₂,RPtHgR′] (R = CH₃, R′= 2,5-C₆H₃Cl₂, 2,3,4- and 2,4,6-C₆H₂Cl₃, 2,3,4,5-, 2,3,4,6- and 2,3,5,6-C₆HCl₄, C₆Cl₅; R = Et, R′ = 2,5-C₆H₃Cl₂, 2,4,6-C₆H₂Cl₃; R = 2-C₆H₄Cl, R′=2-C₆H₄(CH₃)) have been prepared by the reactions of RHgR′ with Pt(PPh₃)₃, in order to study their possible use as intermediates in the preparation of diorganoplatinum complexes with different organic ligands. The dependence of J(³¹P-¹⁹⁵Pt) on slight differences in the electronic character of the ligand R′ in the series of compounds [(PPh₃)₂(CH₃)Pt-HgR′] has been studied.     

Molybdenum and tungsten complexes with the heteroallyl-like Ph2P(O)C(S)NR− (R  Me,Ph) as ligand. X-ray structural analysis of Mo(CO)2(PPh3)(Ph2P(O)C(S)NPh)2 · CH2Cl2; A 4 : 3 piano-stool configuration

Ph₂P(O)C(S)N(H)R (R  Me, Ph) reacts with M(CO)₃(η⁵-C₅H₅)Cl (M  Mo, W) in the presence of Et₃N to give M(CO)₂(η⁵-C₅H₅)(Ph₂P(O)C(S)NR). The deprotonated ligand coordinates in a bidentate manner through N and S to give a four-membered ring system. M(CO)₃(PPh₃)₂Cl₂ (M  Mo, W) reacts with Ph₂P(O)C(S)N(H)R (R  Me, Ph) in the presence of Et₃N to give complexes in which the central metal atoms are seven coordinate through two ligands bonded via O and S to form five-membered ring systems, one PPh₃, and two CO groups. The complexes were characterised by elemental analyses, IR, ¹H NMR, and ³¹P NMR spectroscopy, and an X-ray structural analysis of Mo(CO)₂(PPh₃)(Ph₂P(O)C(S)NPh)₂ · CH₂Cl₂.     

Electrochemical behaviour of [Ru(L)(CO)2Cl2] [Ru(L)(CO)Cl3][Me4N] and [Ru(L)(CO)2(CH3CN)2][CF3SO3]2 complexes (L = 2,2′- bipyridine or 4,4′-isopropoxycarbonyl-2,2′-bipyridine)

The clectrochemical behaviour of the complexes [Ru^II(L)(CO)₂Cl₂], [Ru^II(L)(CO)Cl₃][Me₄N] and [Ru^II(L)(CO)₂(CH₃CN)₂][CF₃SO₃]₂ (L = 2,2′-bipyridine or 4,4′-isopropoxycarbonyl-2,2′-bipyridine) has been investigated in CH₃CN. The oxidation of [Ru(L)(CO)₂Cl₂] produces new complexes [Ru^III(L)(CO)(CH₃CN)₂Cl]²⁺ as a consequence of the instability of the electrogenerated transient Ru^III species [Ru^III(L)(CO)₂Cl₂]⁺. In contrast, the oxidation of [Ru^II(L)(CO)Cl₃][Me₄N] produces the stable [Ru^III(L)(CO)Cl₃] complex. In contrast [Ru^II(L)(CO)₂(CH₃CN)₂][CF₃SO₃]₂ is not oxidized in the range up to the most positive potentials achievable. The reduction of [Ru^II(L)(CO)₂Cl₂] and [Ru^II(L)(CO)₂(CH₃CN)₂][CF₃SO₃]₂ results in the formation of identical dark blue strongly adherent electroactive films. These films exhibit the characteristics of a metal-metal bond dimer structure. No films are obtained on reduction of [Ru^II(L)(CO)Cl₃][Me₄N]. The effect of the substitution of the bipyridine ligand by electron-withdrawing carboxy ester groups on the electrochemical behaviour of all these complexes has also been investigated.     

Reactions of methyl and ethyl halides with the complexes Ni[P(C2H5)3]4 and Ni(X)[P(C2H5)3]3

The rates of the thermal reaction of the nickel(0) complex Ni[P(C₂H₅)₃]₄ with the alkyl halides CH₃Br, CH₃I in toluene have been compared with those of the reactions of the nickel(I) complexes Ni(X)[P(C₂H₅)₃]₃ (X  Br,I). The organic products from CH₃X are methane and ethane, and those from C₂H₅I are ethane and ethylene. The reactivity of the nickel(I) complexes is 10–20 times less than that of the nickel(0) complex. The result suggest that the first step of the reaction of nickel(0) with CH₃I is the expected oxidative addition of the halide to the metal substrate. The intermediate thus formed decomposes to produce ethane (and small amounts of methane) without further reaction with the organic halide. This mechanism is supported by deuterium-labeling experiments.