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1.
《Angewandte Chemie (International ed. in English)》2017,56(42):12925-12929
The reaction of (C5Me5)2Th(CH3)2 with the phosphonium salts [CH3PPh3]X (X=Cl, Br, I) was investigated. When X=Br and I, two equivalents of methane are liberated to afford (C5Me5)2Th[CHPPh3]X, rare terminal phosphorano‐stabilized carbenes with thorium. These complexes feature the shortest thorium–carbon bonds (≈2.30 Å) reported to date, and electronic structure calculations show some degree of multiple bonding. However, when X=Cl, only one equivalent of methane is lost with concomitant formation of benzene from an unstable phosphorus(V) intermediate, yielding (C5Me5)2Th[κ2‐(C,C′)‐(CH2)(CH2)PPh2]Cl. Density functional theory (DFT) investigations of the reaction energy profiles for [CH3PPh3]X, X=Cl and I showed that in the case of iodide, thermodynamics prevents the production of benzene and favors formation of the carbene. 相似文献
2.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(42):13105-13109
The reaction of (C5Me5)2Th(CH3)2 with the phosphonium salts [CH3PPh3]X (X=Cl, Br, I) was investigated. When X=Br and I, two equivalents of methane are liberated to afford (C5Me5)2Th[CHPPh3]X, rare terminal phosphorano‐stabilized carbenes with thorium. These complexes feature the shortest thorium–carbon bonds (≈2.30 Å) reported to date, and electronic structure calculations show some degree of multiple bonding. However, when X=Cl, only one equivalent of methane is lost with concomitant formation of benzene from an unstable phosphorus(V) intermediate, yielding (C5Me5)2Th[κ2‐(C,C′)‐(CH2)(CH2)PPh2]Cl. Density functional theory (DFT) investigations of the reaction energy profiles for [CH3PPh3]X, X=Cl and I showed that in the case of iodide, thermodynamics prevents the production of benzene and favors formation of the carbene. 相似文献
3.
Dieter Naumann Wieland Tyrra Rudolf Herrmann Ingo Pantenburg Mathias S. Wickleder 《无机化学与普通化学杂志》2002,628(4):833-842
Te(C6F5)4 was prepared from the reactions of TeCl4 or Te(C6F5)2Cl2 with Grignard reagents or AgC6F5 in moderate to good yields. Substitution reactions with Me3SiX (X = Cl, Br, OSO2CF3), with equimolar amounts of Br2, with AgNO3 and with H[BF4] or BF3·OEt2 yielded the Te(C6F5)3X derivatives (X = Cl, Br, OSO2CF3, NO3, BF4). Oxidation reactions of Cd, Hg, and Pd0 complexes led to Te(C6F5)2 and the corresponding bis(pentafluorophenyl) derivatives M(C6F5)2 (M = Cd, Hg, Pd) and with InBr to In(C6F5)2Br. From very slow hydrolysis of Te(C6F5)4 the oxide Te(C6F5)2O was prepared. The thermal decomposition, the NMR and mass spectra of the partially new compounds are discussed. The crystal structures of Te(C6F5)3Br (monoclinic, P21/a, Z = 4), [Te(C6F5)3][OSO2CF3] (monoclinic, P21/n, Z = 16) and [Te(C6F5)2O]2 (triclinic, P1¯, Z = 2) were determined. 相似文献
4.
Hypervalent Pentafluoroethylgermanium Compounds, [(C2F5)nGeX5−n]− and [(C2F5)3GeF3]2− (X=F,Cl; n=2–5)
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Dr. Stefanie Pelzer Beate Neumann Dr. Hans‐Georg Stammler Dr. Nikolai Ignat'ev Prof. Dr. Berthold Hoge 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(46):16460-16466
This paper gives an account on hypervalent fluoro‐ and chloro(pentafluoroethyl)germanium compounds. The selective synthesis of the tris(pentafluoroethyl)dichlorogermanate salt [PNP][(C2F5)3GeCl2] as well as its X‐ray structural analysis is described. As a representative example for pentafluoroethylfluorogermanates, the synthesis and structure of 2,4,6‐triphenylpyryliumtris(pentafluoroethyl)difluorogermanate [C23H17O][(C2F5)3GeF2] is reported. Fluoride‐ion affinities for pentafluoroethylgermanes were calculated using quantum chemical methods, disclosing (C2F5)3GeF as a weaker Lewis acid than (C2F5)3SiF or (C2F5)3PF2. The theoretical results were confirmed by experiments and give the basis of a synthetic protocol for (C2F5)3GeF. Pentakis(pentafluoroethyl)germanate [PPh4][Ge(C2F5)5] was detected as an intermediate during the synthesis of [PPh4][(C2F5)4GeF] starting from tris(pentafluoroethyl)difluorogermanate and LiC2F5. 相似文献
5.
Organometallic Compounds of Copper. XVIII. On the Reaction of the Alkyne Copper(I) Complexes [CuX(S‐Alkyne)] (X = Cl, Br, I; S‐Alkyne = 3,3,6,6‐Tetramethyl‐1‐thiacyclohept‐4‐yne) with the Phosphanes PMe3 and Ph2PCH2CH2PPh2 (dppe) The alkyne copper(I) halide complexes [CuX(S‐Alkyne)]n ( 2 ) ( 2 a : X = Cl, 2 b : X = Br, 2 c : X = I; S‐Alkyne = 3,3,6,6‐tetramethyl‐1‐thiacyclohept‐4‐yne; n = 2, ∞) add the phosphanes PMe3 and Ph2PCH2CH2PPh2 (dppe) to form the mono‐ and dinuclear copper compounds [(S‐Alkyne)CuX(PMe3)] ( 6 ) ( 6 a : X = Cl, 6 b : X = Br) and [(S‐Alkyne)CuX(μ‐dppe)CuX(S‐Alkyne)] ( 7 a : X = Cl, 7 b : X = Br, 7 c : X = I), respectively. By‐product in the reaction of 2 a with dppe is the tetranuclear complex [(S‐Alkyne)Cu(μ‐X)2Cu(μ‐dppe)2Cu(μ‐X)2Cu(S‐Alkyne)] ( 8 ). In case of the compounds 7 prolonged reaction times yield the alkyne‐free dinuclear copper complexes [Cu2X2(dppe)3] ( 9 ) ( 9 a : X = Cl, 9 b : X = Br, 9 c : X = I)). X‐ray diffraction studies were carried out with the new compounds 6 a , 6 b , 7 b , 8 , and 9 c . 相似文献
6.
Heteronuclear Metal Atom Clusters of the Types X4?n[SnM(CO)4P(C6H5)3]n and M2(CO)8[μ-Sn(X)M(CO)4P(C6H5)3]2 by Reaction of SnX2 with M2(CO)8[P(C6H5)3]2 (X = Halogene; M = Mn, Re; n = 2, 3) The compounds of the both types X4?n[SnM(CO)4P(C6H5)3]n (n = 3; M = Mn; X = F, Cl, Br, I. n = 2: M = Mn, Re; X = Cl, Br, I) and M2(CO)8[μ-Sn(X)M(CO)4P(C6H5)3]2 (M = Mn; X = Cl, I. M = Re; X = Cl, Br, I) are prepared by reaction of SnX2 with M2(CO)8[P(C6H5)3]2 (M = Mn, Re). Their IR frequencies are assigned. In Re2(CO)8[μ-Sn(Cl)Re(CO)4P(C6H5)3]2 the central molecule fragment contains a planar Re2Sn2 rhombus with a transannular Re? Re bond of 316.0(2) pm. Each of the SnIV atoms is connected with the terminal ligands Cl and Re(CO)4P(C6H5)3. These ligands are in transposition with respect to the Re2Sn2 ring. The mean values for the remaining bond distances (pm) are: Sn? Re = 274.0(3); Sn? Cl = 243(1), Re? C = 176(5), Re? P = 242.4(9), C? O = 123(5). The factors with an influence on the geometrical shape of such M2Sn2 rings (M = transition metal) are discussed. 相似文献
7.
Summary Nitrosyl chloride has been treated with [Ni(PPh3)2X2] (X = Cl, Br, NCS or NO3) to obtain [Ni(PPh3)XCl]2 (X=Cl, Br, NCS or NO3) and [Ni(OPPh3)(SCN)Cl]2. The compounds obtained were characterised by analyses, infrared (including far i.r.) and visible spectral studies, magnetic moment and conductivity measurements and many chemical reactions. It is proposed that the compounds have a dimeric structure with a distorted tetrahedral environment around the nickel atom and chloro-bridges. 相似文献
8.
Hans‐Christian Bttcher Marion Graf Kurt Merzweiler Christoph Wagner 《无机化学与普通化学杂志》2000,626(2):597-603
Coordinatively Unsaturated Diruthenium Complexes: Synthesis and X‐Ray Crystal Structures of [Ru2(CO)4(μ‐H)(μ‐S)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)], [Ru2(CO)4(μ‐X)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] (X = Cl, S2CH) [Ru2(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 1 ) reacts in benzene with elemental sulfur to the addition product [Ru2(CO)4(μ‐H)(μ‐S)(μ‐PtBu2)(μ‐dppm)] ( 2 ) (dppm = Ph2PCH2PPh2). 2 is also obtained by reaction of 1 with ethylene sulfide. The reaction of 1 with carbon disulfide yields with insertion of the CS2 into the Ru2(μ‐H) bridge the dithioformato complex [Ru2(CO)4(μ‐S2CH)(μ‐PtBu2)(μ‐dppm)] ( 3 ). Furthermore, 1 reacts with [NO][BF4] to the complex salt [Ru2(CO)4(μ‐NO)(μ‐H)(μ‐PtBu2)(μ‐dppm)][BF4] ( 4 ), and reaction of 1 with CCl4 or CHCl3 affords spontaneously [Ru2(CO)4(μ‐Cl)(μ‐PtBu2)(μ‐dppm)] ( 5 ) in nearly quantitative yield. The molecular structures of 2 , 3 and 5 were confirmed by crystal structure analyses. 相似文献
9.
Magnesium Phthalocyanines: Synthesis and Properties of Halophthalocyaninatomagnesate, [Mg(X)Pc2?]? (X = F, Cl, Br); Crystal Structure of Bis(triphenylphosphine)iminiumchloro-(phthalocyaninato)magnesate Acetone Solvate Magnesium phthalocyanine reacts with excess tetra(n-butyl)ammonium- or bis(triphenylphosphine)iminiumhalide ((nBu4N)X or (PNP)X; X = F, Cl, Br) yielding halophthalocyaninatomagnesate ([Mg(X)Pc2?]?; X = F, Cl, Br), which crystallizes in part as a scarcely soluble (nBu4N) or (PNP) complex-salt. Single-crystal X-ray diffraction analysis of b(PNP)[Mg(Cl)Pc2?] · CH3COCH3 reveals that the Mg atom has a tetragonal pyramidal coordination geometry with the Mg atom displaced out of the center (Ct) of the inner nitrogen atoms (Niso) of the nonplanar Pc ligand toward the Cl atom (d(Mg? Ct) = 0.572(3) Å; d(Mg? Cl) = 2.367(2) Å). The average Mg? Niso distance is 2.058 Å. Pairs of partially overlapping anions are present. The cation adopts a bent conformation (b(PNP)+: d(P1? N(K)) = 1.568(3) Å; d(P2? N(K)) = 1.587(3) Å; ?(P1? N(K)? P2) = 141.3(2)°). Electrochemical and spectroscopic properties are discussed. 相似文献
10.
Structures of Bis(trifluoromethyl)halogeno and thiocyanato Mercurates, [Hg(CF3)2X]— (X = Br, I, SCN), and a Comparison of the Structural Parameters of the CF3 Groups [(18‐C‐6)K]2[Hg(CF3)2SCN]2 (1) and [P(CH3)(C6H5)3]2[Hg(CF3)2X]2 (X = Br (2) , I (3) ) are prepared and their crystal structures are determined. [(18‐C‐6)K]2[Hg(CF3)2SCN]2 (1) crystallizes in the monoclinic space group P21/c with Z = 2, [P(CH3)(C6H5)3]2[Hg(CF3)2Br]2 (2) in the monoclinic space group P21/n with Z = 2 and [P(CH3)(C6H5)3]2[Hg(CF3)2I]2 (3) in the triclinic space group P1¯ with Z = 1. In the solid state the three compounds form dimeric anions with planar Hg2X2 rings. The structural parameters of the Hg(CF3)2 units in the till now known bis(trifluoromethyl)halogeno mercurates are compared. In all compounds one nearly symmetric and one distorted CF3 group exist. The largest differences of the C—F bond lengths is found for [(18‐C‐6)K][Hg(CF3)2I]. This can be regarded as the experimental evidence for the properties of trifluoromethyl mercury compounds to act as excellent difluorocarbene sources in the presence of alkali iodides. 相似文献
11.
Reduction of various pentafluorophenylnickel(II) complexes in the presence of phosphines gives unstable nickel(I) compounds but Ni(C6F5)(CO)2(PPh3)2 is isolated in the presence of CO. Similar NiR(CO)2(PPh3)2 (R = C6F5,C6Cl5, 2,3,5,6-C6Cl4H) are obtained by reaction of the halogenonickel(I) complex with MgRBr or LiR. Reduction of NiX2L2 in the presence of acetylenes gives [NiXL2]2(μ-PhCCR) (R = H, X = Cl and R = Ph, X = Cl, Br) when L = P-n-Bu3 but only NiX(PPh3)3 are recovered when L = PPh3. No reaction with the alkyne is observed for [NiX(PPh3)2]n but [NiCl(PPh3)]n reacts with RCCR′ to give paramagnetic NiCl(PPh3)(CRCR′) (R = Ph, R′= H, COOEt), diamagnetic [NiCl(PPh3)]2(μ-PhCCPh) and cyclotrimerization when R = R′ = COOMe. Chemical and structural behaviour of the new nickel(I) complexes is described. 相似文献
12.
U. Baumeister H. Hartung A. Krug K. Merzweiler T. Schulz C. Wagner H. Weichmann 《无机化学与普通化学杂志》2000,626(10):2185-2195
Ligand Behaviour of P‐functional Organotin Halides: Nickel(II), Palladium(II), and Platinum(II) Complexes with Me2(Cl)SnCH2CH2PPh2 Me2(Cl)SnCH2CH2PPh2 ( 1 ) reacts with NiII, PdII, and PtII halides in molar ratio 2 : 1 forming the complexes [MX2{PPh2CH2CH2Sn(Cl)Me2}2] (M = Ni, Pd, Pt; X = Cl, Br) ( 3 – 6 , 9 , 10 ) ( 7 , 8 : M = Ni; Br instead of Cl). The nickel complexes were isolated and characterized both as the planar ( 3 , 5 , 7 ) and the tetrahedral ( 4 , 6 , 8 ) isomer. Crystal structure analyses and NMR data indicate for the planar nickel complexes 3 , 5 , 7 and [MCl2{PPh2CH2CH2Sn(Cl)Me2}2] ( 9 : M = Pd; 10 : M = Pt) the existence of intra and intermolecular M–Hal…Sn bridges. In a ligand : metal molar ratio of 3 : 1 the complexes [MéCl{PPh2CH2CH2Sn⊖Cl2Me2}{PPh2CH2CH2Sn(Cl)Me2}2] ( 11 : M = Pd; 12 : M = Pt) are formed which represent intramolecular ion pairs. By dehalogenation of [PdCl2{PPh2CH2CH2Sn(Cl)Me2}2] ( 9 ) with sodium amalgam and graphite potassium (C8K), respectively, the palladacycles cis‐[Pd{PPh2CH2CH2SnMe2}2] ( 13 ) and trans‐[Pd(Cl)PPh2CH2CH2SnMe2{PPh2CH2CH2Sn(Cl)Me2}] ( 14 ) are formed. From the compounds 1 , 3 , 9 , 11 , and 12 the crystal structures are determined. All compounds are characterized by 1H, 31P, and 119Sn NMR spectroscopy. 相似文献
13.
Azido Beryllates with Adamantan‐like Structures: Synthesis, IR Spectra, and Crystal Structures of (Ph4P)2[Be4X4(μ‐N3)6] (X = Cl, Br) The azido beryllates (Ph4P)2[Be4X4(μ‐N3)6] (X = Cl 1a , X = Br 1b ) have been prepared by the reaction of Me3SiN3 with the halogeno beryllates (Ph4P)2[Be2Cl6] and (Ph4P)2[Be2Br6], respectively, in CH2Cl2 and CH2Br2 solution, respectively. Both complexes form moisture sensitive, colourless crystals, which are nonexplosive with respect to mechanical or thermal stress. They are characterized by IR spectroscopy and by crystal structure determinations. 1a and 1b crystallize isotypically in the space group C2/c with 12 formula units per unit cell. Whereas 1a was only refined to R1 = 0.13, which is caused by disordering, 1b could be refined to R1 = 0.066. The structures contain adamantanlike dianions [Be4X4(μ‐N3)6]2— with two symmetry nonequivalent individuals which differ only slightly from one another. The Be4N6 core is formed by bridging function of the α‐nitrogen atoms of the azide groups with BeN bond lengths of 172.5 and bond lengths Nα—Nβ = 123.2 pm and Nβ—Nγ = 113.1 pm on average in the structure of 1b . 相似文献
14.
Reactions of copper(I) halides (Cl, Br, I) with 1‐methyl‐1, 3‐imidazoline‐2‐thione (mimzSH) in 1 : 2 molar ratio yielded sulfur‐bridged dinuclear [Cu2X2(μ‐S‐mimzSH)2(η1‐S‐mimzSH)2] (X = I, 1 , Br, 2 ; Cl, 3 ) complexes. Copper(I) iodide with 1,3‐imidazoline‐2‐thione (imzSH2) and Ph3P in 1 : 1 : 1 molar ratio has also formed a sulfur‐bridged dinuclear [Cu2I2(μ‐S‐imzSH2)2(PPh3)2] ( 4 ) complex. The central Cu(μ‐S)2Cu cores form parallelograms with unequal Cu–S bond distances {2.324(2), 2.454(3) Å} ( 1 ); {2.3118(6), 2.5098(6) Å} ( 2 ); {2.3075(4), 2.5218(4) Å} ( 3 ); {2.3711(8), 2.4473(8) Å} ( 4 ). The Cu···Cu separations, 2.759–2.877Å in complexes 1 – 3 are much shorter than 3.3446Å in complex 4 . The weak intermolecular interactions {H2CH···S# ( 2 ); CH···Cl# ( 3 ); NH···I# ( 4 )} between dimeric units in complexes 2 – 4 lead to the formation of linear 1D polymers. 相似文献
15.
《Journal of organometallic chemistry》2004,689(12):2080-2086
The reaction of [Pt2(μ-S)2(P-P)2] (P-P=2PPh3, 2PMe2Ph, dppf) [dppf=1,1′-bis(diphenylphosphino)ferrocene] with cis-[M(C6F5)2(PhCN)2] (M=Ni, Pd) or cis-[Pt(C6F5)2(THF)2] (THF=tetrahydrofuran) afforded sulfide aggregates of the type [{Pt2(μ3-S)2(P-P)2}M(C6F5)2] (M=Ni, Pd, Pt). X-ray crystal analysis revealed that [{Pt2(μ3-S)2(dppf)2}Pd(C6F5)2], [{Pt2(μ3-S)2(PPh3)2}Ni(C6F5)2], [{Pt2(μ3-S)2(PPh3)2}Pd(C6F5)2] and [{Pt2(μ3-S)2(PMe2Ph)2}Pt(C6F5)2] have triangular M3S2 core structures capped on both sides by μ3-sulfido ligands. The structural features of these polymetallic complexes are described. Some of them display short metal-metal contacts. 相似文献
16.
The Dihydridoiridium(III) Complex [IrH2Cl(P i Pr3)2] as a Molecular Building Block for Unsymmetrical Binuclear Rhodium–Iridium and Iridium–Iridium Compounds The title compound [IrH2Cl(PiPr3)2] ( 3 ) reacts with the chloro‐bridged dimers [RhCl(PiPr3)2]2 ( 1 ) and [IrCl(C8H14)(PiPr3)]2 ( 5 ) by cleavage of the Cl‐bridges to give the unsymmetrical binuclear complexes 4 and 6 with Rh(μ‐Cl)2Ir and Ir(μ‐Cl)2Ir as the central building block. The reactions of 3 with the bis(cyclooctene) and (1,5‐cyclooctadiene) compounds [MCl(C8H14)2]2 ( 7 , 8 ) and [MCl(η4‐C8H12)]2 ( 9 , 10 ) (M = Rh, Ir) occur analogously and afford the rhodium(I)‐iridium(III) and iridium(I)‐iridium(III) complexes 11 – 14 in 70–80% yield. Treatment of [(η4‐C8H12)M(μ‐Cl)2IrH2(PiPr3)2] ( 13 , 14 ) with phenylacetylene leads to the formation of the substitution products [(η4‐C8H12)M(μ‐Cl)2IrH(C≡CPh)(PiPr3)2] ( 15 , 16 ) without changing the central molecular core. Similarly, the compound [(η4‐C8H12)Rh(μ‐Br)2IrH(C≡CPh)(PiPr3)2] ( 18 ) has been prepared; it was characterized by X‐ray crystallography. 相似文献
17.
Reactions of the oxorhenium(V) complexes [ReOX3(PPh3)2] (X = Cl, Br) with the N‐heterocyclic carbene (NHC) 1,3,4‐triphenyl‐1,2,4‐triazol‐5‐ylidene (LPh) under mild conditions and in the presence of MeOH or water give [ReOX2(Y)(PPh3)(LPh)] complexes (X = Cl, Br; Y = OMe, OH). Attempted reactions of the carbene precursor 5‐methoxy‐1,3,4‐triphenyl‐4,5‐dihydro‐1H‐1,2,4‐triazole ( 1 ) with [ReOCl3(PPh3)2] or [NBu4][ReOCl4] in boiling xylene resulted in protonation of the intermediately formed carbene and decomposition products such as [HLPh][ReOCl4(OPPh3)], [HLPh][ReOCl4(OH2)] or [HLPh][ReO4] were isolated. The neutral [ReOX2(Y)(PPh3)(HLPh)] complexes are purple, airstable solids. The bulky NHC ligands coordinate monodentate and in cis‐position to PPh3. The relatively long Re–C bond lengths of approximate 2.1Å indicate metal‐carbon single bonds. 相似文献
18.
Chiral Half‐sandwich Pentamethylcyclopentadienyl Rhodium(III) and Iridium(III) Complexes with Schiff Bases from Salicylaldehyde and α‐Amino Acid Esters [1] A series of diastereoisomeric half‐sandwich complexes with Schiff bases from salicylaldehyde and L‐α‐amino acid esters including chiral metal atoms, [(η5‐C5H5)(Cl)M(N,O‐Schiff base)], has been obtained from chloro bridged complexes [(η5‐C5Me5)(Cl)M(μ‐Cl)]2 (M = Rh, Ir). Abstraction of chloride from these complexes with Ag[BF4] or Ag[SO3CF3] affords the highly sensitive compounds [(η5‐C5Me5)M(N,O‐Schiff base]+X? (M = Rh, Ir; X = BF4, CF3SO3) to which PPh3 can be added under formation of [(η5‐C5Me5)M(PPh3)(N,O‐Schiff base)]+X?. The diastereoisomeric ratio of the complexes ( 1 ‐ 7 and 11 ‐ 12 ) has been determined from NMR spectra. 相似文献
19.
In(C6F5)3 · CH3CN and In(C6F5)3 · glyme were synthesized from InCl3 and Cd(C6F5)2 in CH3CN or glyme in 43% and 35% yield, respectively. Replacement of CH3CN or (C2H5)2O by DMAP yielded the corresponding 1 : 1-adduct. [PNP][In(C6F5)4] was best prepared from the corresponding cesium salt which was best synthesized from the reaction of stoichiometric amounts of In(C6F5)3 · CH3CN, (CH3)3 SiC6F5 and CsF in good yield. [PNP][In(C6F5)4] crystallizes in the triclinic space group P 1, a = 1104.9(4) pm, b = 1442.4(6) pm, c = 1833.8(8) pm, α = 110.87(2)°, β = 92.04(3)°, γ = 96.55(3)°, Z = 2. 相似文献
20.
Three dinuclear copper(I) complexes, [Cu2(µ‐Cl)2(1,2‐(PPh2)2‐1,2‐C2B10H10)2]·2CH2Cl2 ( 1 ), [Cu2(µ‐Br)2(1,2‐(PPh2)2‐1,2‐C2B10H10)2]·2THF ( 2 ) and {Cu2(µ‐I)2[1,2‐(PPh2)2‐1,2‐C2B10H10]2} ( 3 ) have been synthesized by the reactions of CuX (X = Cl, Br and I) with the closo ligand 1,2‐(PPh2)2‐1,2‐C2B10H10. All these complexes were characterized by elemental analysis, FT‐IR, 1H and 13C NMR spectroscopy and X‐ray structure determination. Single crystal X‐ray structure determinations show that every complex contained di‐µ‐X‐bridged structure involving a crossed parallelogram plane formed by two Cu atoms and two X atoms (X = Cl, Br, I). The geometry at the Cu atom was a distorted tetrahedron, in which two positions were occupied by two P atoms of the PPh2 groups connected to the two C atoms of carborane (Cc), and the other two resulted from two X atoms which bridged the other Cu atom at the same time. To the best of our knowledge, this is the first example of copper(I) complexes with 1,2‐diphenylphosphino‐1,2‐dicarba‐closo‐dodecaborane as ligand characterized by X‐ray diffraction. The catalytic property of the complex 3 for the amination of iodobenzene with aniline was also investigated. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献