Characterization of [Re2Cl3(μ-dppm)2(NCCH3)2][Cl] and [Re2Cl3(μ-dppm)2(NCC6H5)2][Cl]·2CH2Cl2 by X-ray Crystallographic and Two-Dimensional NMR Spectroscopic Techniques

The complex Re₂Cl₆(P-n-Bu₃)₂ prepared in situ reacts with CH₃CN to form a blue-green solution. Addition of the chelating phosphine bis(diphenylphosphino)methane (dppm) results in the formation of the complex [Re₂Cl₃(-dppm)₂(NCCH₃)₂][Cl] (1) upon heating. The two acetonitrile molecules adopt a trans geometry on the rhenium center with the axially coordinated chlorine. The analogous trans benzonitrile species [Re₂Cl₃(-dppm)₂(NCC₆H₅)₂][Cl]·2CH₂Cl₂ (2) is synthesized under the same reaction conditions. The coupling constants of the AABB ³¹P{¹H} NMR spectra of the compounds were elucidated from ³¹P–³¹P homonuclear J-resolved NMR experiments. Additional characterization methods include ³¹P{¹H} NMR spectroscopy, UV-vis spectroscopy, and X-ray crystallography.     

Reactions of the dirhenium(II) complexes Re2X4(dppm)2 (X= Cl,Br; dppm = Ph2PCH2PPh2) with isocyanides. Part IX. New isomeric forms of the mixed carbonyl-isocyanide dirhenium(II) Complexes Re2 Cl4(dppm)2(CO)(CNxyl) and [Re2Cl3(dppm)2(CO)(CNxyl)2]O3SCF3 The X-ray crystal structure of [(xyl NC)2ClRe(μ-dppm)2ReCl2(CO)] O3SCF3

The monocarbonyl complex Re₂Cl₄(µ-dppm)₂(CO) reacts with xylyl isocyanide in acetonitrile to afford the bioctahedral complex (CO)Cl₂Re(µ-dppm)₂ ReCl₂(CNxyl), 2b. This is a different structural isomer from the edge-sharing bioctahedral complex Cl₂Re(µ-Cl)(µ-dppm)₂ReCl(CNxyl) or this same stoichiometry which A formed when acetone is be reaction solvent. The complex2b reacts with a further equivalent of xylNC in the presence of TlO₃SCF₃ in dichloromethane to form a red complex of composition [Re₂Cl₃(µ-dppm)₂ (CO)(CNxyl)₂]O₃SCF₃. 3, which has the open bioctahedral structure [(xylNC)₂ClRe(µ-dppm)₂ReCl₂(CO)]O₃SCF₃. This is a third isomeric form of this dirhenium cation: the previously isolated green and yellow forms have edge-sharing bioctahedral structures. Crystal data for3 at 295 K: orthorhombic space group Pbca (No. 61) witha=22.654(5) Å,b=22.717(4) Å,c=27.324(4) A,V= 14061(7) ų, andZ = 8. The structure was refined to R = 0.059 (R, = 0.134 ) for 14164 data. The Re-Re distance is 2.3833(8) Å.     

Synthesis and structure of [Re3S3.7Br4.3(PPh3)3]·0.5CH2Cl2

One of the products of the reaction between Re₃S₇Br₇ and PPh₃ has been isolated in crystalline state and characterized by single crystal X-ray diffraction (XRD), mass-spectrometry, and EPR spectroscopy. The crystalline phase obtained is a co-crystallization product of two cluster complexes: [Re₃(μ₃-S)₂(μ-S)₂(μ-Br)Br₃(PPh₃)₃] (1a) an [Re₃(μ₃-S)₂(μ-S)(μ-Br)₂Br₃(PPh₃)₃] (1b). The ratio 1a:1b in the investigated single crystal sample is ～7:3.     

(Ph3P)2,Co(CO)2Cl和(dppe-P,P)2CO(CO)+的分子轨道研究

本文对(PH3P)2, Co(CO)2Cl和(dppe-P,P)2CO(CO)+(dppe=Ph2CH2CH2PPh2)五配位C2O对称性模型化合物进行了分轨道研究, 结果表明, 钴的3d轨道很少参与成键, 钴的4s, 4P与配体的S,P轨道通过形式上的二电子三中心键和二电子二中心键的相互作用构成五配位, 此外, 还解释了这两种化合物不同稳定性的原因。     

Chlorine reaction with platinum triamine [Pt(N,N-DimeTm)PyCl3]Cl (N,N-DimeTm = (CH3)2N(CH2)3NH2). Crystal structure of [Pt(N,N-DimeTm)Cl2], [Pt(N,N-DimeTm(Py)Cl3]Cl · H2O and [Pt{(CH3)2N(CH2)2C(O)NH}(Py)Cl3]

Treatment of platinum(II) diamine [Pt(N,N-DimeTm)Cl₂] (I) with pyridine gave tetramine [Pt(N,N-DimeTm)Py₂]Cl₂ (II); by oxidation with chlorine this was converted to Pt(IV) triamine, [Pt“(N,N-DimeTm(Py)Cl₃]Cl (III) with a six-membered chelate ring. According to X-ray diffraction data, the reaction of complex II with chlorine is accompanied by removal of the pyridine molecule from the trans-position to the NH₂ group of N,N-dimethyltrimethylenediamine. The reaction of complex III with chlorine at 20°C afforded a mixture of compounds (IV) and the complex [Pt“(CH₃)₂N(CH₂)₂C(O)NH”(Py)Cl₃] (V) with an amidate six-membered metal ring, dimethylpropioamide, which was also isolated upon refluxing a mixture of IV in an aqueous solution. The UV/Vis and IR spectra of the obtained complexes were studied, and X-ray diffraction analysis of I, III, and V was performed. The crystals of I are triclinic, space group P $ \bar 1 $ ; a = 7.6526(4) Å, b = 11.5571(6) Å, c = 12.4432(7) Å, α = 113.85(1)°, β = 96.54(2)°, γ = 106.78(2)°; Z = 4; R _hkl = 0.051. The crystals of III are monoclinic, space group C2/c; a = 36.715(2) Å, b = 7.8179(4) Å, c = 29.721(16) Å, β = 127.80(1)°; Z = 16; R _hkl = 0.036. The crystals of V are monoclinic, space group P2₁/n; a = 7.0398(6) Å, b = 27.458(2) Å, c = 7.687(6) Å, β = 106.270(1)°; Z = 4; R _hkl = 0.052.     

The excited-state geometry of [Re2Cl8]2−

We report the luminescence spectrum of a single crystal of [Bu₄N]₂[Re₂Cl₈] at ≈20 K. The spectrum shows progressions in the Re-Re stretching vibration v₁ based on an electronic origin at 14161 cm⁻¹ and on false origins. The luminescence spectrum exhibits a “mirror-image” relationship to the absorption spectrum and is interpreted as showing that the transition originates from the ¹δδ¹ excited state of the eclipsed ion.     

Synthesis and Crystal Structure of [Pd(NH_3)_4]Cl_2·2[Pd(NH_3)_3Cl]Cl

PreparahonofsomecomplexcomPOundsof[Pd(NH3)41X2tw,tvhereX=Cl-,Br,I-,X2=Co,:-,RdChl'-,etc.,wasdescribedasearlyl942l'].SynthesisandcryStalstIUCtUreOfthesaltSt'ithamons,Cr2o7",Cro.:',MoO"',andC,o'=',ttcrestillreportedmorcrecenh/'-'j.IPd(NH)4lX2,tvhereX=Cl',BrandNOz,isanotherkindofamndnepalladiumcomplexcompounds.IntheSyStemofIPd(NH).1"-Cl'-H2o,diamlltinedichloridepalladium(II)wasObtalnedbythereachonOfIPd(NH)4lHcomplexionwtthanutebydrogenchloride,andtetrachloridepalladiumaDbythe…     

Synthesis of Dimethyl Carbonate from CO2 , Methanol, and Epoxides Using Re（CO） 5 Cl/K2 CO3 as Catalyst System

IntroductionOver the past few years, dimethyl carbonate(DMC) has been proven to be an efficientmethylating,methoxylating, and methoxycarbonylating agent inorganic syntheses, in which DMC is used to replace thetoxic methyl halides, dimethyl sulfate or carb     

Photocatalytic reduction of CO2 using cis,trans-[Re(dmbpy)(CO)2(PR3)(PR’3)]+ (dmbpy=4,4′-dimethyl-2,2′-bipyridine)

Photocatalysis of biscarbonylrhenium complexes cis,trans-[Re(dmbpy)(CO)₂(PR₃) (PR′₃)]⁺ (dmbpy=4,4′-dimethyl-2,2′-bipyridine: R, R′=Ph (1a ⁺); p-FPh (1b ⁺); R=Ph, R′=OEt (1c ⁺); R, R′=O-i-Pr (1d ⁺)) is reported for the first time. The rhenium complexes with two triarylphosphine ligands (1a ⁺, 1b ⁺) efficiently photocatalyzed CO₂ reduction with triethanolamine as a sacrificial donor. On the other hand, the complexes with one or two trialkylphosphite ligand(s) (1c ⁺, 1d ⁺) had low photocatalytic abilities under the same reaction conditions.     

Fe3(CO)8[P[SC6H5)Cl2](μ3-S)2的合成和晶体结构

The title compound Fe_3(CO)_8 (P(SC_6H_5) Cl_2) (μ_3′-S)_2 was synthesised by reacting Fe_3(CO)_9 (μ_3-S)_2 with P (SC_6H_5) Cl_2. The crystal and molecular structure of the title compound has been determined by single crystal diffraction method. Crystal data: triclinic, space group P1, with a=0.7571(1), b=0.9097(1), c=1.7706(2) nm, α=95.03(1), β=101.79(1), γ=105.73(1)°, V =1.1359 nm, Z=2, Dc=1.935 g·cm~(-3). The structure was solved by direct method and difference Fourier synthesis, and refined by full-matrix least-squares with anisotropic thermal paramaters for non-hydrogen atoms, using 3724 observed reflections withI≥3σ(I). The final residual factor R=0.025, R_W=0.028.Fe_(CO)_8(P(SC_6H_5)Cl_2)(μ_3-s)_2 has a face-bridged 4e donors and the monosubstituted ligand is on the apical Fe atom.     

The unusual stability of [NpO2Cl4]2−: Synthesis and characterisation of [NpO2(DPPMO2)2Cl]2[NpO2Cl4] and [Ph3PNH2]2[NpO2Cl4]

The [NpO₂(DPPMO₂)₂Cl][NpO₂Cl₄] complex (where DPPMO₂ = bis(diphenylphosphino)methanedioxide) contains the linear neptunyl group, {NpO₂}²⁺, with two bidentate P=O donor ligands. Coordinating anion Cl^? fills the fifth equatorial coordination site yielding a complex of general formula [NpO₂(DPPMO₂)₂X]₂[Y] (1) (where X = Cl^? and Y = [NpO₂Cl₄]^2?. Reaction between our newly prepared neptunium starting material [NpO₂Cl₂(thf)]_n and phosphinimine ligand produced crystals of [Ph₃PNH₂]₂[NpO₂Cl₄] (2). Compounds 1 and 2 have been structurally characterised.     

Synthesis, crystal and molecular structures of an isomorphic N, S-bridged [Cu2(μ2-I)2(PPh3)2(μ2-N, S-pymSH)] dimer and S-bonded [CuX(η1-S-pymSH)(PPh3)2] monomers (X = Cl, Br)

Abstract  Monoclinic crystals of [Cu₂(μ-I)₂(PPh₃)₂(μ-N, S-pymSH)] · CH₃CN) (1), were obtained by equimolar reaction of copper(I) iodide with pyrimidine-2-thione (pymSH), followed by the addition of triphenylphosphine (PPh₃) in acetonitrile. Crystal data for 1: space group P2₁, Z = 2, a = 9.896, b = 18.378, c = 11.703 ?, β = 101.73°. It has an iodo-bridged Cu(μ-I)₂Cu core and the pyrimdine-2-thione binds to both Cu centers via N, S-bridging across the Cu(μ-I)₂Cu core. This N, S-bridging, a rare coordination mode for pyrimidine-2-thione, leads to a short Cu···Cu separation of 2.675(2) ? (sum of van der Waals radius of Cu atoms, 2.80 ?). The geometry around each Cu center is distorted tetrahedral with angles varying in the range, ca. 102–119°. Copper(I) chloride and bromide also yielded monoclinic crystals of S-bonded tetrahedral monomers, [CuBr(pymSH)(PPh₃)₂] 2 and [CuCl(pymSH)(PPh₃)₂] 3. Crystal data for 2: space group P2₁/n, Z = 8, a = 12.825, b = 43.122, c = 13.396 ?, β = 90.79°. Crystal data for 3: space group P2₁/c, Z = 4, a = 14.340, b = 10.111, c = 24.200 ?, β = 94.36°. Compound 2 has two crystallographically independent molecules in crystal lattice. The ³¹P NMR spectrum of 1 showed two signals for PPh₃ ligands bonded to two Cu centers with different coordination cores: CuI₂PN and CuI₂PS. Both 2 and 3 showed one signal each for PPh₃ in their ³¹P NMR spectra. Graphical abstract  Reaction of copper(I) iodide with pyrimidine-2-thione and triphenylphosphine formed monoclinic crystals of dimer 1 with unusual N, S-bridging across Cu(μ₂-I)₂Cu core.      

New routes to carbonyl complexes of general formula [RuCl2(CO)(S)(PPh3)2] (S = DMA,DMF, DMSO): crystal structure of [RuCl2(CO)(DMA)(PPh3)2] · 1/2CH2Cl2

The compound [RuCl₂(CO)(DMA)(PPh₃)₂] [DMA = dimethylacetamide] was obtained from [RuCl₃(PPh₃)₂-(DMA)] · DMA and CO in DMA. Orange crystals of [RuCl₂(CO)(DMA)(PPh₃)₂] · 1/2CH₂Cl₂ were isolated by slow evaporation of a CH₂Cl₂/DMA solution and its structure was determined by single crystal X-ray diffraction. The analogous compounds containing DMF and DMSO were obtained from the precursor ttt-[RuCl₂(CO)₂(PPh₃)₂]. Characterization of the other complexes is based on i.r. and n.m.r. spectroscopy, including ³¹P{¹H} data.     

Synthesis,crystal structure and Raman spectra of [dabcoH2]CuICl3, [dabcoH2]3Cl4CuIICl4(DMSO) and Cu3Cl3(dabco)(DMSO) (dabco = 1,4-diazabicyclo [2.2.2] octane)

Dissolving elemental copper in a CCl₄–DMSO mixture in the presence of dabco (dabco = 1,4-diazabicyclo [2.2.2] octane) resulted in the formation of a compound with the composition [dabcoH₂][CuCl₃] featuring a univalent copper salt. This compound, composed of discrete dabcoH₂²⁺ cations and CuCl₃^2? anions, represents the first example of a copper(I) chloride derivative containing a doubly protonated [dabcoH₂]²⁺ unit, and a very rare example of the oxidative dissolving of copper in a CCl₄–DMSO mixture to give a Cu(I) compound. The addition of some drops of water to the initial reaction mixture led to the formation of the [dabcoH₂]₃Cl₄CuCl₄(DMSO). Three [dabcoH₂]²⁺ units and four Cl^? anions, bound via N–H…Cl hydrogen bonds, form a horseshoe-like cationic fragment. The divalent copper ion possesses a rather unusual pseudo-tetrahedral surrounding. The comproportionation reaction of CuCl₂·2H₂O and copper powder in the presence of dabco in DMSO results in the formation of the Cu₃Cl₃(dabco)(DMSO) complex. Copper and chlorine ions form unprecedented Cu₆Cl₆ cores, interconnected by neutral dabco linkers into infinite 2-D layers. All the compounds were characterized using the single-crystal X-ray diffraction technique and Raman spectroscopy.     

[Co^I(CO)(dppe-P,P')2]2[Co2^I^I(μ-dppeo)Cl6].2CH3OH的合成和结构

合成了混合价态多核羰基钴离子对配合物[Co^I/(CO)(dppe-P,P')2]2[co2^I^I(μ-dppeo)Cl6]{dppeo=双二苯基膦基乙烷Ph2P(O)CH2CH2P(O)Ph2},用X射线衍射法测定了其晶体学参数为a=11.761(3),b=12.860(2), c=21.428(3)A, a=81.45(2), β=82.47(2), γ=79.84(2)°, 三斜晶系, PI空间群, Co^I和Co^I^I具有不同的配位构型, 量子化学计算结果解释了该配合物稳定的原因。     

Mixed Amidohalotantalates [Ta(NMe2)3X3]– (X = F,Cl)

Russian Journal of Coordination Chemistry - The anionic tantalum complex (ItBuH)[Ta(NMe2)3Cl3] (I) is synthesized by the reaction of [Ta(NMe2)3Cl2]2 with N-heterocyclic carbene ItBu and is isolated...