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1.
The carbamoyl complex [C(NMe2)3][(CO)4Fe{C(O)NMe2}] ( 1 ) reacts with InMe3 under loss of the methyl groups to produce a variety of compounds from which only the anionic cluster complexes [C(NMe2)3]3[Fe2(CO)6(μ‐CO){μ‐InFe(CO)4(μ‐O2CNMe2)InFe(CO)4}] ([C N 3]3[ 2 ]) and [C(NMe2)3]2[{(CO)4Fe}2In(O2CNMe2)]·THF ([C N 3]2[ 3 ]·THF) could be crystallized and characterized by X‐ray analyses. The anion [ 2 ]3? has a Fe2(CO)9‐like structure and both anions contain the carbaminato ligand either in a bridging or in a chelating function.  相似文献   

2.
Concerning the Reaction of Cp2TiCl2 with [C(NMe2)3][(CO)4FeC(O)NMe2] – Crystal Structure of [C(NMe2)3]2[FeCl4] The title compound forms by the reaction of Cp2TiCl2 with [C(NMe2)3][(CO)4FeC(O)NMe2] in THF solution. It crystallizes in the space group Pbcn with a = 1 566.6(3); b = 976.4(2); c = 1 580.4(4) pm; Z = 4; R = 3.8%. Each [FeCl4]2? in is surrounded by eight cations. Two cations each are connected with one Cl atom by relatively short H …? Cl contacts leading to a distortion of the tetrahedral geometry of the anion.  相似文献   

3.
Preparation, Structure, and Quantum Chemical Calculation of [C(NMe2)3]2[(CO)4FeInCl3] The title compound ( 1 ) has been obtained as colorless crystals by reacting InCl3 with [C(NMe2)3][(CO)4FeC(O)NMe2] in THF solution. The crystal structure determination (monoclinic, C2/c) shows the presence of separate ions with one disordered and one non disordered cation. In the dianion the CO groups of the trigonal bipyramidal coordinated iron atom and the Cl atoms of the tetrahedral coordinated indium atom form a staggered conformation with a relatively short In–Fe bond distance of 252 pm. Quantum Chemical DFT calculations of [CO)4FeInCl3]2– show that the Fe–In bond has a strong ionic character and that it should be considered as an adduct of [Fe(CO)4]2– and InCl3.  相似文献   

4.
The reaction between the salt like iron carbamoyl complex [C(NMe2)3][(CO)4FeC(O)NMe2] ( 1 ) and InBr3 proceeds with formation of an iron indium bond to give the salt [C(NMe2)3]2[(CO)4FeInBr3] ( 2 ). InI3, however, acts as an oxidation agent to produce with 1 the intercalation compound [FeI2]2 · [MeN=C(NMe2)2] ( 3 ) as main product. Minor amounts of the penta‐metallic neutral complex [{(CO)3Fe(μ‐C(NMe2)O)2Fe(CO)2C(NMe2)O}2Fe] ( 4 ) and the indium containing salt [C(NMe2)3][(CO)4Fe(μ‐InI2)2NMe2] ( 5 ) were also isolated and characterized by X‐ray analyses.  相似文献   

5.
The Reactions of CH2=P(NMe2)3 with Fe(CO)5, Cr(CO)6, and CS2; Molecular Structures of [MeP(NMe2)3][(CO)5CrC(O)CH=P(NMe2)3], and (CO)4Fe=C(OMe)CH=P(NMe2)3 The ylide CH2=P(NMe2)3 ( 1 ) reacts with several binary transition metal carbonyls M(CO)x to produce the corresponding salt like compounds [MeP(NMe2)3][(CO)x–1MC(O)CH=P(NMe2)3] (M = Fe ( 3 ), Cr ( 4 )). The related reaction with CS2 leads to the salt [MeP(NMe2)3][SC(S)CH=P(NMe2)3] ( 2 ). While 4 is thermally stable, 3 rapidly decomposes at room temperature with formation of [MeP(NMe2)3]2[Fe2(CO)8] ( 8 ). Alkylation of 3 (at –50 °C) and 4 with MeSO3CF3 produces the related carbene complexes (CO)x–1M=C(OMe)CH=P(NMe2)3 ( 5 ) and ( 6 ); the reaction of 3 with Me3SiCl results in the formation of the carbene complex (CO)4Fe=C(OSiMe3)CH=P(NMe2)3 ( 7 ). 4 crystallizes in the space group P212121 (No. 19) with a = 1111.1(2), b = 1476.1(3), c = 1823.1(4) pm and Z = 4. 5 crystallizes in the space group P21/n (No. 14) with a = 1303.6(3), b = 910.5(4), c = 1627.0(4) pm, β = 96.06(2)° and Z = 4. The compounds have been characterized by elemental analyses, NMR (1H, 13C, 31P) and IR spectroscopy.  相似文献   

6.
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   

7.
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   

8.
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   

9.
Synthesis and Crystal Structure of [C(NMe2)3]2[(CO)4Fe(μ‐InCl2)2Fe(CO)4] Treatment of [C(NMe2)3]2[(CO)4FeInCl3] ( 1 ) with hot water produces the dinuclear complex [C(NMe2)3]2[(CO)4Fe(μ‐InCl2)2Fe(CO)4] ( 2 ) which could be crystallized from dichloromethane/pentane. 2 crystallizes in the monoclinic space group P21/n with a = 835.7(1), b = 1187.8(1), c = 1902.7(1) pm, β = 91.877(5)° and Z = 2. The anion contains a four‐membered Fe—In—Fe—In ring with octahedral environment at the iron atom and tetrahedral coordination at the In atom.  相似文献   

10.
Preparation, Structures, and Properties of Tris-hexamethyl-trisila-tetraphospha-nortricyclene-bis-chromiumtricarbonyl [P4(Sime2)3]3[Cr(CO)3]2 Hexamethyl-trisila-tetraphospha-nortricyclene P4(Sime2)3 1 reacts with C6H6Cr(CO)3 or (CHT)Cr(CO)3 (CHT ? Cycloheptatriene) under formation of [P4(Sime2)3]3[Cr(CO)3]2 3 (red crystals), in which each of the Cr atoms is attached to one P atom of a P3 ring of the three molecules 1 . 3 can also be prepared by heating a solution of P4(Sime2)3Cr(CO)5 in benzene or THF up to 120–1307deg;C. The compound 3 crystallizes in an orthorhombic and a hexagonal form, the latter being stabilized by one mole toluene. As revealed by single crystal investigations, the symmetry ¯6, distances and angles are nearly unchanged. The o-form corresponds to a face centered cubic packing of the molecules, whereas the h-form is hexagonal close packed.  相似文献   

11.
Solvent-free Synthesis of Tetramethylammonium Salts: Synthesis and Characterization of [N(CH3)4]2[C2O4], [N(CH3)4][CO3CH3], [N(CH3)4][NO2], [N(CH3)4][CO2H], and [N(CH3)4][O2C(CH2)2CO2CH3] A general procedure to synthesize tetramethylammonium salts is presented. Several tetramethylammonium salts were prepared in a crystalline state by solvent-free reaction of trimethylamine and different methyl compounds at mild conditions: [N(CH3)4]2[C2O4] (cubic; a = 1 114.8(3) pm), [N(CH3)4][CO3CH3] (P21/n; a = 813.64(3), b = 953.36(3), c = 1 131.3(4) pm, β = 90.03(1)°), [N(CH3)4][NO2] (Pmmn; a = 821.2(4), b = 746.5(3), c = 551.5(2) pm), [N(CH3)4][CO2H] (Pmmn; a = 792.8(7), b = 791.7(3), c = 563.3(4) pm) and [N(CH3)4][O2C(CH2)2CO2CH3] (P21; a = 731.1(2), b = 826.4(3), c = 1 025.2(3) pm, β = 110.1(1)°). The tetramethylammonium salts were characterized by IR-spectroscopy and X-ray diffraction. The crystal structures of the methylcarbonate and the nitrite are described.  相似文献   

12.
Bis(dimethylamino)trifluoro sulfonium Salts: [CF3S(NMe2)2]+[Me3SiF2], [CF3S(NMe2)2]+ [HF2] and [CF3S(NMe2)2]+[CF3S] From the reaction of CF3SF3 with an excess of Me2NSiMe3 [CF3(NMe2)2]+[Me3SiF2] (CF3‐BAS‐fluoride) ( 5 ), from CF3SF3/CF3SSCF3 and Me2NSiMe3 [CF3S(NMe2)2]+‐ [CF3S] ( 7 ) are isolated. Thermal decomposition of 5 gives [CF3S(NMe2)2]+ [HF2] ( 6 ). Reaction pathways are discussed, the structures of 5 ‐ 7 are reported.  相似文献   

13.
Syntheses and Crystal Structures of new Amido- und Imidobridged Cobalt Clusters: [Li(THF)2]3[Co32-NHMes)3Cl6] (1), [Li(DME)3]2[Co184-NPh)33-NPh)12Cl3] (2), [Li(DME)3]2[Co64-NPh)(μ2-NPh)6(PPh2Et)2] (3), and [Li(THF)4][Co83-NPh)62-NPh)3(PPh3)2] (4) The reactions of cobalt(II)-chloride with the lithium-amides LiNHMes and Li2NPh leads to an amido-bridged multinuclear complex [Li(THF)2]3[Co32-NHMes)3Cl6] ( 1 ) as well as to the imido-bridged cobalt cluster [Li(DME)3]2[Co184-NPh)33-NPh)12Cl3] ( 2 ). In the presence of tertiary phosphines two imido-bridged cobalt clusters [Li(DME)3]2[Co64-NPh)(μ2-NPh)6(PPh2Et)2] ( 3 ) and [Li(THF)4][Co83-NPh)62-NPh)3(PPh3)2] ( 4 ) result. The structures of 1 – 4 were characterized by X-ray single crystal structure analysis.  相似文献   

14.
Crystal Structures of Octacyanomolybdates(IV). IV Dodecahedral [Mo(CN)8] Coordination of the Cyano‐Bridged Cobalt and Nickel Ammin Complexes MII2(NH3)8[Mo(CN)8] · 1.5 H2O (MII = Co, Ni) and Ni2(NH3)9[Mo(CN)8] · 2 H2O At single crystals of the hydrated cyano complexes Co2(NH3)8[Mo(CN)8] · 1.5 H2O (a = 910.0(4), b = 1671(2), c = 1501(1) pm, β = 93.76(6)°) and Ni2(NH3)8[Mo(CN)8] · 1.5 H2O (a = 899.9(9), b = 1654.7(4), c = 1488(1) pm, β = 94.01°), isostructurally crystallizing in space group P21/c, Z = 4, and of trigonal Ni2(NH3)9[Mo(CN)8] · 2 H2O (a = 955.1(1), c = 2326.7(7) pm, P31, Z = 3), X‐ray structure determinations were performed at 168 resp. 153 K. The [Mo(CN)8]4– groups of the three compounds, prepared at about 275 K and easily decomposing, show but slightly distorted dodecahedral coordination (mean distances Mo–C: 216.3, 215.4 and 216.1 pm). Within the monoclinic complexes the anions twodimensionally form cyano bridges to the ammin cations [M(NH3)4]2+ and are connected with the resulting [MN6] octahedra (Co–N: 215.1 pm, Ni–N: 209.8 pm) into strongly puckered layers. The trigonal complex exhibits a chain structure, as one [Ni(NH3)5]2+ cation is only bound as terminal octahedron (Ni–N: 212.0 pm). Details and the influence of hydrogen bridges are discussed.  相似文献   

15.
A fully encapsulated Pt 4 tetrahedron in an incomplete tetrahedron of 36 nickel atoms is present in [Ni36Pt4(CO)45]6− ( 1 ; see picture for the metal framework), which is obtained as an inseparable mixture with [Ni37Pt4(CO)46]6− ( 2 ) by reaction of [Ni6(CO)12]2− with K2[PtCl4]. The trimethylbenzylammonium salts of 1 and 2 cocrystallize in a 1:1 ratio. The additional Ni atom of 2 caps the truncated vertex of 1 .  相似文献   

16.
Synthesis, Structure, and Reactivity of the Ferrioarsaalkene [(η5‐C5Me5)(CO)2FeAs=C(Ph)NMe2] Reaction of equimolar amounts of the carbenium iodide [Me2N(Ph)CSMe]I and LiAs(SiMe3)2 · 1.5 THF afforded the thermolabile arsaalkene Me3SiAs = C(Ph)NMe2 ( 1 ), which in situ was converted into the black crystalline ferrioarsaalkene [(η5‐C5Me5)(CO)2FeAs=C(Ph)NMe2)] ( 2 ) by treatment with [(η5‐C5Me5)(CO)2FeCl]. Compound 2 was protonated by ethereal HBF4 to yield [(η5‐C5Me5)(CO)2FeAs(H)C(Ph)NMe2]BF4 ( 3 ) and methylated by CF3SO3Me to give [(η5‐C5Me5)(CO)2FeAs(Me)C(Ph)NMe2]‐ SO3CF3 ( 4 ). [(η5‐C5Me5)(CO)2FeAs[M(CO)n]C(Ph)NMe2] ( 5 : [M(CO)n] = [Fe(CO)4]; 6 : [Cr(CO)5]) were isolated from the reaction of 2 with [Fe2(CO)9] or [{(Z)‐cyclooctene}Cr(CO)5], respectively. Compounds 2 – 6 were characterized by means of elemental analyses and spectroscopy (IR, 1H, 13C{1H}‐NMR). The molecular structure of 2 was determined by X‐ray diffraction analysis.  相似文献   

17.
On the Crystal Structures of the Cyano Complexes [Co(NH3)6][Fe(CN)6], [Co(NH3)6]2[Ni(CN)4]3 · 2 H2O, and [Cu(en)2][Ni(CN)4] Of the three title compounds X‐ray structure determinations were performed with single crystals. [Co(NH3)6][Fe(CN)6] (a = 1098.6(6), c = 1084.6(6) pm, R3, Z = 3) crystallizes with the CsCl‐like [Co(NH3)6][Co(CN)6] type structure. [Co(NH3)6]2[Ni(CN)4]3 · 2 H2O (a = 805.7(5), b = 855.7(5), c = 1205.3(7) pm, α = 86.32(3), β = 100.13(3), γ = 90.54(3)°, P1, Z = 1) exhibits a related cation lattice, the one cavity of which is occupied by one anion and 2 H2O, whereas the other contains two anions parallel to each other with distance Ni…Ni: 423,3 pm. For [Cu(en)2][Ni(CN)4] (a = 650.5(3), b = 729.0(3), c = 796.5(4) pm, α = 106.67(2), β = 91.46(3), γ = 106.96(2)°, P1, Z = 1) the results of a structure determination published earlier have been confirmed. The compound is weakly paramagnetic and obeys the Curie‐Weiss law in the range T < 100 K. The distances within the complex ions of the compounds investigated (Co–N: 195.7 and 196.4 pm, Ni–C: 186.4 and 186.9 pm, resp.) and their hydrogen bridge relations are discussed.  相似文献   

18.
New Phosphorus-bridged Transition Metal Carbonyl Complexes. The Crystal Structures of [Re2(CO)7(PtBu)3], [Co4(CO)10(PtBu)2], [Ir4(CO)6(PtBu)6], and [Ni4(CO)10(PiPr)6], (PtBu)3 reacts with [Mn2(CO)10], [Re2(CO)10], [Co2(CO)8] and [Ir4(CO)12] to form the multinuclear complexes [M2(CO)7(PtBu)3] (M = Re ( 1 ), Mn ( 5 )), [Co4(CO)10(PtBu)2] ( 2 ) and [Ir4(CO)6(PtBu)6] ( 3 ). The reaction of (PiPr)3 with [Ni(CO)4] leads to the tetranuclear cluster [Ni4(CO)10(PiPr)6] ( 4 ). The complex structures were obtained by X-ray single crystal structure analysis: ( 1 : space group P1 (Nr. 2), Z = 2, a = 917.8(3) pm, b = 926.4(3) pm, c = 1 705.6(7) pm, α = 79.75(3)°, β = 85.21(3)°, γ = 66.33(2)°; 2 : space group C2/c (Nr. 15), Z = 4, a = 1 347.7(6) pm, b = 1 032.0(3) pm, c = 1 935.6(8) pm, β = 105.67(2)°; 3 : space group P1 (Nr. 2), Z = 4, a = 1 096.7(4)pm, b = 1 889.8(10)pm, c = 2 485.1(12) pm, α = 75.79(3)°, β = 84.29(3)°, γ = 74.96(3)°; 4 : space group P21/c (Nr. 14), Z = 4, a = 2 002.8(5) pm, b = 1 137.2(8) pm, c = 1 872.5(5) pm, β = 95.52(2)°).  相似文献   

19.
Syntheses and Crystal Structure Analyses of [SbI3(SbMe3)(THF)]2 and [Li(THF)4]2[Bi2Cl8(THF)2] The reaction of Me3Sb with SbI3 in tetrahydrofuran (THF) gives [SbI3(SbMe3)(THF)]2 ( 1 ). [Li(THF)4]2[Bi2Cl8(THF)2] ( 2 ) is formed by reaction of LiCl and BiCl3 in tetrahydrofuran. The structures of ( 1 ) and ( 2 ) have been determined by X-ray diffractometry. Both structures contain centrosymmetric dimers with the geometry of edge sharing octahedra.  相似文献   

20.
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   

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