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1.
To provide a better understanding of the recently published pure metalorganic NiI species, [Ni(cod)2][Al(ORF)4] ( 1 ) [cod = 1,5‐cyclooctadiene, RF = C(CF3)3], further characterizations were performed and analyzed. Thus, the solvation of 1 in THF was examined by EPR, surprisingly disclosing the initiation of a disproportionation reaction to [NiII(THF)6][Al(ORF)4]2 ( 3 ) and Ni0. Further studies concerning the ability of 1 to activate small molecules exhibit the formation of a remarkable [Ni3S2(cod)3]2+ cluster ( 5 ) in an oxidation reaction with S8, while EPR measurements of the resulting product in a reaction with oxygen indicate a possible coordination of O2. Single crystal X‐ray structures as well as spectroscopic analyses of 3 and 5 are described.  相似文献   

2.
The crystal structures of two square tetracyanocomplexes were determined. [Ni(dien)2][Ni(CN)4]·2H2O (NDNCH) and [Ni‐(dien)2][Pd(CN)4] (NDPC) (dien = diethylene triamine) exhibit ionic structures consisting of mer‐[Ni(dien)2]2+ cations and [Ni(CN)4]2‐ or [Pd(CN)4]2‐ anions, respectively. Moreover, the structure of NDNCH is completed by two water molecules of crystallisation. In both compounds hydrogen bonds contribute to the stabilisation of the structure. NDNCH dehydrates on air quickly yielding anhydrous [Ni(dien)2][Ni(CN)4] (NDNC). Its thermal decomposition proceeds in a complicated process followed by aerial oxidation of metallic nickel to NiO.  相似文献   

3.
Derivatives of the Fluorite Type: [Fe(NH3)6][TaF6]2 and [Ni(NH3)6][TaF6]2 Light blue single crystals of [Fe(NH3)6][TaF6]2 and [Ni(NH3)6][TaF6]2 are obtained from 36 : 1 : 6 molar mixtures of (NH4)F, iron/nickel and tantalum powders, respectively, in sealed Monel metal ampoules at 400 °C. They both crystallize isotypic with [Co(NH3)6][PF6]2 (cubic, Fm-3m, Z = 4, a = 1259.0(2)/1260.4(2) pm) in a structure that can be derived from the basic fluorite-type of structure according to [Ca][F]2≡[Fe(NH3)6][TaF6]2, for example.  相似文献   

4.
The reaction of the NHC iPr2Im [NHC=N‐heterocyclic carbene, iPr2Im = 1, 3‐bis(isopropyl)imidazolin‐2‐ylidene] with freshly prepared NiBr2 in thf or dme results in the formation of the air stable nickel(II) complex trans‐[Ni(iPr2Im)2Br2] ( 2 ). Complex 2 was structurally characterized. Thermal analysis (DTA/TG) reveals a very high decomposition temperature of 298 °C. Reduction of 2 with sodium or C8K in the presence of the olefins COD (cyclooctadiene) or COE (cyclooctene) affords the highly reactive compounds [Ni2(iPr2Im)4(COD)] ( 1 ) and [Ni(iPr2Im)2(COE)] ( 4 ). Alkylation of 2 with organolithiums leads to the formation of trans‐[Ni(iPr2Im)2(R)2] [R = Me ( 5 ), CH2SiMe3 ( 6 )], whereas the reaction of 2 with LiCp* [Cp* = (η5‐C5(CH3)5)] at 80 °C causes the loss of one NHC ligand and affords [(η5‐C5(CH3)5)Ni(iPr2Im)Br] ( 7 ).  相似文献   

5.
Reaction of C(NMe2)4 with Ni(CO)4 – Syntheses and Structures of [C(NMe2)3][(CO)3NiC(O)NMe2], [C(NMe2)3]2[Ni5(CO)12], and [C(NMe2)3]3[Ni6(CO)12][O2CNMe2] The reaction of C(NMe2)4 with Ni(CO)4 in THF produces the carbamoyl complex [C(NMe2)3][(CO)3NiC(O)NMe2] ( 1 ); side products are the purple cluster compound [C(NMe2)3]2[Ni5(CO)12] · THF ( 2 · THF) and the red cocristallization product [C(NMe2)3]3[Ni6(CO)12][O2CNMe2] ( 3 ). All compounds were studied by X‐ray diffraction analyses. The cations of 3 are all disordered but not those of 1 and 2 . The unit cell of 1 contains two crystallographically independent anions (I and II) which differ in the dihedral angle between the plane of the carbamoyl ligand and the plane defined by the atoms CCarbamoyl–Ni–CO amounting 0° in the anion I and 18° in the anion II.  相似文献   

6.
Syntheses and Crystal Structures of Chalcogenido‐bridged Nickel Cluster Compounds [Ni5Se4Cl2(PPhEt2)6], [Ni12Se12(PnPr3)6], and [Ni18S18(PiPr3)6] The reaction of (R)ESiMe3 (R = SiMe3, Mes = C9H11; E = S, Se) with [NiCl2(PPhEt2)2] and [NiCl2(PR3)2] (R = nPr, iPr) gives new chalcogenido‐bridged nickel cluster compounds [Ni5Se4Cl2(PPhEt2)6]·2THF ( 1 ), [Ni12Se12(PnPr3)6]·2THF ( 2 ), and [Ni18S18(PiPr3)6]·2THF ( 3 ). The structures of these compounds were determined by single crystal X‐ray structural analyses.  相似文献   

7.
The reaction of 1,1-diethyl-3-(4-fluorobenzoyl)-thiourea (HL) with CuCl2 ·?2H2O and NiCl2 ·?6H2O give two complexes, Cu(HL)3Cl (1) and NiL2 (2). The crystal structures of these products were determined by single crystal X-ray diffraction. In 1, three HL molecules are unidentate, coordinating through the sulfur, and the copper is tetrahedral with three S and one Cl. In 2, two HL molecules are O and S donor bidentate and coordinate as anionic species with loss of the proton from the acyl-substituted nitrogen; the nickel is square-planar.  相似文献   

8.
We herein showcase the ability of NHC‐coordinated dinuclear NiI–NiI complexes to override fundamental reactivity limits of mononuclear (NHC)Ni0 catalysts in cross‐couplings. This is demonstrated with the development of a chemoselective trifluoromethylselenolation of aryl iodides catalyzed by a NiI dimer. A novel SeCF3‐bridged NiI dimer was isolated and shown to selectively react with Ar−I bonds. Our computational and experimental reactivity data suggest dinuclear NiI catalysis to be operative. The corresponding Ni0 species, on the other hand, suffers from preferred reaction with the product, ArSeCF3, over productive cross‐coupling and is hence inactive.  相似文献   

9.
合成了马来二氰基二硫烯镍(Ⅱ)配合物,[2-Na Phth Me Py NH2]2[Ni(mnt)2]([2-Na Phth Me Py NH2]+为1-(2'-萘苄基)-2-氨基吡啶鎓离子),并用元素分析,UV,IR,单晶X-射线衍射表征了其组成和结构。结果表明,配合物系单斜晶系,空间群P21/c,a=13.335(2),b=7.9458(12),c=17.480(3),α=90°,β=97.646(2)°,γ=90°,V=1835.7(5),Z=2。  相似文献   

10.
A series of fourteen octahedral nickel(IV) dithiocarbamato complexes of the general formula [Ni(ndtc)3]X·yH2O {ndtc stands for the appropriate dithiocarbamate anion, X stands for ClO4 (1-8; y = 0) or [FeCl4] (9-14; y = 0 for 9-12, 1 for 13 and 0.5 for 14} was prepared by the oxidation of the corresponding nickel(II) complexes, i.e. [Ni(ndtc)2], with NOClO4 or FeCl3. The complexes, involving a high-valent NiIVS6 core, were characterized by elemental analysis (C, H, N, Cl and Ni), UV-Vis and FTIR spectroscopy, thermal analysis and magnetochemical and conductivity measurements. The X-ray structure of [Ni(hmidtc)3][FeCl4] (9) was determined {it consists of covalently discrete complex [Ni(hmidtc)3]+ cations and [FeCl4] anions} and this revealed slightly distorted octahedral and tetrahedral geometries within the complex cations, and anions, respectively. The Ni(IV) atom is six-coordinated by three bidentate S-donor hexamethyleneiminedithiocarbamate anions (hmidtc), with Ni-S bond lengths ranging from 2.2597(5) to 2.2652(5) Å, while the shortest Ni···Cl and Ni···Fe distances equal 4.1043(12), and 6.2862(6) Å, respectively. Moreover, the formal oxidation state of iron in [FeCl4] as well as the coordination geometry in its vicinity was also proved by 57Fe Mössbauer spectroscopy in the case of 9.  相似文献   

11.
A New Aluminum/Nickel/Oxo‐Cluster: [Ni(acac)OAl(OtBu)2]4 When bis(tert‐butoxy)alane (tBu‐O)2AlH is allowed to react with nickeldiacetylacetonate at elevated temperature a new nickel/aluminum/oxo cluster [Ni(acac)OAl(OtBu)2]4 is formed together with aluminum acetylacetonate Al(acac)3 and some other products. The metal/oxo cluster is isolated by crystallization and structurally fully characterized by X‐ray diffraction analysis. The molecule [Ni(acac)OAl(OtBu)2]4 contains an eight membered Al4O4 cycle, to which eight mutually edge sharing NiO2Al cycles are fused. The overall point symmetry of the metal/oxo cluster is almost S4. While the aluminum atoms are tetrahedrally surrounded by oxygen ligands (mean distances Al‐O in‐between 1, 730(6) and 1, 789(6) Å)), the nickel atoms are in a square pyramidal coordination sphere of oxygen atoms (Ni‐Oaxial = 1.938(6) Å, Ni‐Obasal = 2.056(9) Å; all polyhedra are distorted). The nickel atoms have a d8 high spin electron configuration (μeff = 3.32 B.M.).  相似文献   

12.
Synthesis and Structure Investigations of Iodocuprates(I). XV Iodocuprate(I) with Solvated Cations: [Li(CH3CN)4] [Cu2I3] and [Mg{(CH3)2CO}6][Cu2I4] [Li(CH3CN)4][Cu2I3] 1 and [Mg((CH3)2CO)6][Cu2I4] 2 were prepared by reactions of CuI with LiI in acetonitrile and of CuI with MgI2 in acetone. 1 crystallizes orthorhombic, Pnma, a = 552.7(2), b = 1258.8(8), c = 2516(1) pm, z = 4. [Li(CH3CN)4]+ cations are located between rod packings of CuI4 tetrahedra double chains [(CuI2/2I2/4)2]? parallel to the axis. Short intermolecular anion/cation contacts were observed. The crystal structure of 2 (monoclinic, P21/n, a = 1840(2), b = 1059.2(2), c = 1879(2)pm, β = 112.94(4)°, z = 4) is built up by [Mg((CH3)2CO)6]2+ cations forming a simple hexagonal sphere packing. The binuclear anions [Cu2I4]2? occupy holes in the trigonal prismatic channels formed by the cations.  相似文献   

13.
Preparation and Crystal Structures of Ag[N(CN)2](PPh3)2, Cu[N(CN)2](PPh3)2, and Ag[N(CN)2](PPh3)3 The coordination compounds Ag[N(CN)2](PPh3)2 ( 1 ), Cu[N(CN)2](PPh3)2 ( 2 ), and Ag[N(CN)2](PPh3)3 ( 3 ) are obtained by the reaction of AgN(CN)2 or CuN(CN)2 with triphenylphosphane in CH2Cl2. X‐ray structure determinations were performed on single crystals of 1 , 2 , and 3 · C6H5Cl. The three compounds crystallize monoclinic in the space group P21/n with the following unit cell parameters. 1 : a = 1216.07(9), b = 1299.5(2), c = 2148.4(3) pm, β = 99.689(13)°, Z = 4; 2 : a = 1369.22(10), b = 1257.29(5), c = 1888.04(15) pm, β = 94.395(7)°, Z = 4; 3 · C6H5Cl: a = 1276.6(4), b = 1971.7(3), c = 2141.3(5) pm, β = 98.50(3)°, Z = 4. In all structures the metal atoms have a distorted tetrahedral coordination. The crystal structure of 3 · C6H5Cl shows monomeric molecular units with terminal coordinated dicyanamide. The crystal structure of 1 is built up by dinuclear units, which are bridged by dicyanamide ligands. However, the crystal structure of 2 corresponds to a onedimensional coordination polymer, bridged by dicyanamide anions.  相似文献   

14.
Phosphoraneiminato‐ and Phosphaneimine Complexes of Nickel(II). Crystal Structures of [Ni(O3SCF3)(NPMe3)]4, [Ni4Br5{NP(NMe2)3}3], [NiBr2{HNP(NMe2)3}2], and [Ni(PMePh2)4] Black‐violet single crystals of [Ni(O3SCF3)(NPMe3)]4 ( 1 ) have been prepared from [NiBr(NPMe3)]4 and copper(I)triflate by metathesis reaction. The nickel atoms are associated via μ3‐N bridges of the (NPMe3) groups to form a heterocubane. The triflate ions are bonded to the Ni atoms in a chelate fashion. Blue single crystals of [Ni4Br5{NP(NMe2)3}3] ( 2 ) are obtained by the reaction of NiBr2 with Me3SiNP(NMe2)3 in boiling toluene in the presence of sodium fluoride. The Ni atoms in 2 are associated with three μ3‐bridged nitrogen atoms of the (NP(NMe2)3) groups as well as by a μ3‐Br atom to give a distorted heterocubane. Deep blue single crystals of the phosphaneimine complex [NiBr2{HNP(NMe2)3}2] ( 3 ) are formed from Me3SiNP(NMe2)3 and NiBr2 in boiling dichloromethane. In 3 the Ni atom is tetrahedrally coordinated by the bromine atoms and by the nitrogen atoms of the phosphane imine molecules. Pale red crystals of [Ni(PMePh2)4] ( 4 ) have been obtained by the reaction of [NiBr(NPMe3)]4 with lithium phenylacetilyde in the presence of PMePh2. In 4 the Ni atom is distorted tetrahedrally coordinated by the phosphorus atoms of the phosphane molecules with Ni–P distances of 219.9 pm in average. 1 – 4 have been characterized by crystallographic X‐ray analyses. 1 : Space group P21/n, Z = 4, lattice dimensions at 193 K: a = 1566.7(2); b = 1479.9(1); c = 1960.6(2) pm; β = 105.908(9)°; R = 0.0443. 2 · 3 CH2Cl2: Space group P21/c, Z = 4, lattice dimensions at 293 K: a = 1226.0(3); b = 1614.0(3); c = 2406.0(5) pm; β = 92.34(3)°; R = 0.0703. 3 : Space group C2/c, Z = 4, latttice dimensions at 203 K: a = 1840.7(1); b = 810.1(1); c = 1607.2(2) pm; β = 94.74(1)°, R = 0.0340. 4 : Space group P1, Z = 2, lattice dimensions at 223 K: a = 1053.1(2); b = 1315.0(3); c = 1674.5(3) pm; α = 81.55(1)°; β = 79.15(2)°; γ = 84.91(2)°; R = 0.0497.  相似文献   

15.
NiCl2 · 6 H2O readily reacts with PPh2NHPh in the presence of zinc dust to yield the homoleptic nickel(0) tetrakis‐phosphine complex [Ni(PPh2NHPh)4] ( 1 ). 1 crystallises triclinic P1 (no. 2), with a = 14.656(1), b = 17.124(2), c = 17.424(1) Å, α = 95.998(1), β = 111.845(1), γ = 111.402(1)°, V = 3630.04(5) Å3, Z = 2, R values [I > 2σ(I)]: R1 = 0.0554, all data: wR2 = 0.1720. The nickel atom is coordinated in a distorted tetrahedral fashion by four phosphorus atoms, resembling a compressed tetrahedron along one of the non‐crystallographic S4 axes.  相似文献   

16.
Crystal Structures of trans ‐[NiBr2(pyridine)4] and [Ni(HNPEt3)4]I2 Turquoise single crystals of trans‐[NiBr2(pyridine)4] have been obtained by the reaction of excess pyridine with nickel(II) bromide/diacetonealcohol. According to the crystal structure determination the nickel atom is octahedrally coordinated by the two bromine atoms in trans‐position and by the nitrogen atoms of the pyridine molecules. Space group Pna21, Z = 4, lattice dimensions at 20 °C: a = 1592.9(2), b = 943.8(1), c = 1413.0(2) pm, R1 = 0.0492. Dark blue single crystals of the phosphoraneimine complex [Ni(HNPEt3)4]I2 have been obtained from NiI2/H2O with excess Me3SiNPEt3 and subsequent recrystallization from acetonitrile. According to the crystal structure determination the nickel atom is tetrahedrally coordinated by the nitrogen atoms of the HNPEt3 molecules. The iodide ions are connected via N–H…I contacts with the cation to form an ion triple. Space group P21/c, Z = 4, lattice dimensions at –80 °C: a = 1934.9(2), b = 1078.3(1), c = 1966.3(2) pm, β = 111.040(8)°; R1 = 0.043.  相似文献   

17.
Addition of NOBF4 to fac-[PPN][Fe(CO)3(TePh)3] in THF at ambient temperature results in formation of Fe2(μ-TePh)2(NO)4l Fe2(?TePh)2(CO)6 and organic products. Methylation of fac-[PPN][Fe(CO)3- (TePh)3] by Mel or [Me3O][BF4] leads to the known dimer Fe2(μ.-TePh)2(CO)6 and organic products. Fe2(μ-TePh)2(NO)4 crystallizes in the orthorhombic space group P bca, with a = 12.701(5) Å, b = 6.7935(16) Å, c = 21.299(9) Å, V = 1837.8(11) Å3, and Z = 4. The core geometry of Fe2(μ-TePh)2(NO)4 is best described as a Fe2Te2 planar rhombus with Te-Fe-Te bond angle 112.09(4)°. A Fe-Fe bond (length 2.827(2) Å) is proposed for Fe2(μ-TePh)2(NO)4 on the basis of the 18-electron rule. The iron atom adopts a distorted tetrahedral geometry with acute bridge Fe-Te-Fe angles 67.91(3)°, and bridging Fe-Te bond of length 2.53(1) Å.  相似文献   

18.
Cyclopropyltetrazole (C3tz) and its nickel(II) and copper(II) complexes [M(C3tz)6](BF4)2] were isolated and characterized by elemental analyses, electronic spectroscopy, molar conductances, magnetic susceptibilities and single-crystal X-ray analyses.  相似文献   

19.
20.
Reaction of NiCl2 with PhP(SiMe3)2, The Crystal Structure of [Ni12Cl2(PPh)2(P2Ph2)4(PHPh)8] [Ni12Cl2(PPh)2(P2Ph2)4(PHPh)8] ( 1 ) has been prepared by the reaction of NiCl2 with PhP(SiMe3)2. The structure has been characterized by X-ray crystal structure analysis. 1 contains a Ni12-cluster with m?4-PPh- and m?6-P2Ph2- as bridging ligands. The terminal PHPh- and Cl-ligands are bound to Ni-atoms. The Ni12-cluster can be described as an Ni8-cube, in which four edges are bridged by Ni-atoms.  相似文献   

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