共查询到20条相似文献,搜索用时 0 毫秒
1.
Copper(I)-acetonitrile complexes are exceedingly useful starting materials for the synthesis of copper(I) complexes with polydentate ligands. To extend the utility of such chemistry to solution studies in relatively low-dielectric solvents (i.e., diethyl ether, toluene) and to aid in obtaining products amenable to X-ray diffraction studies, we have recently begun to employ counteranions such as B(C(6)F(5))(4)(-) for bioinorganic studies. Thus, the synthesis of [Cu(MeCN)(4)]B(C(6)F(5))(4) (1) is presented. Its recrystallization from CH(2)Cl(2)/pentane yields the linear, two-coordinate complex [Cu(MeCN)(2)]B(C(6)F(5))(4) (2), whose centrosymmetric X-ray structure shows that its Cu-N distance is significantly shorter than that in other two-coordinate Cu(I) complexes with nitrogen ligands or that in the tetrahedral complex [Cu(MeCN)(4)]ClO(4). Infrared spectroscopy indicates interesting and diagnostically useful differences between the nu(CN) of 1 and 2. 相似文献
2.
Water- and air-stable complexes comprising the cis-[Re(CO)(2)](+) core can be synthesized from the (Et(4)N)[ReBr(2)(NCCH(3))(2)(CO)(2)] precursor . Complex showed distinctly different chemical and electronic behaviour compared to [ReBr(3)(CO)(3)](2-). Substituting the two bromides in with imidazole-like ligands or alpha,alpha'-diimines gave new complexes with potential applications in bioinorganic chemistry and photochemistry. The two acetonitrile ligands are very stably bound and could not be replaced. Under CO pressure, the uncommon complex mer-[ReBr(NCCH(3))(2)(CO)(3)] was formed from . The reaction of with the tetradentate ligand bis(2-pyridylmethyl)glycine (BPG) finally induced a four fold substitution at the metal center to form a [Re(CO)(2)(L(4))](+)-type complex. 相似文献
3.
A theoretical study including full geometry optimizations is carried out at the IMOMM(MP2:MM3) (IMOMM = integrated molecular orbital molecular mechanics) computational level on the [ReH(5)(PPh(i)()Pr(2))(2)(SiHPh(2))(2)] and [ReH(5)(PCyp(3))(2)(SiH(2)Ph)(2)] systems, the results being compared with available experimental diffraction data, as well as with MP2 results on the model system [ReH(5)(PH(3))(2)(SiH(3))(2)]. A simple scheme for the analysis of the relative weight of different contributions to the "steric" distortion is also proposed and applied to the same [ReH(5)(PPh(i)()Pr(2))(2)(SiHPh(2))(2)] and [ReH(5)(PCyp(3))(2)(SiH(2)Ph)(2)] species. 相似文献
4.
5.
6.
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
7.
The reaction between 1.5 equiv of elemental iodine and rare earth metals in powder form in THF at room temperature gives the rare earth triiodides LnI(3)(THF)(n)() in good yields. Purification by Soxhlet extraction of the crude solids with THF reliably gives the THF adducts LnI(3)(THF)(4) [Ln = La, Pr] and LnI(3)(THF)(3.5) [Ln = Nd, Sm, Gd, Dy, Er, Tm, Y] as microcrystalline solids. X-ray crystallography reveals that the early, larger lanthanide iodide PrI(3)(THF)(4) crystallizes as discrete molecules having a pentagonal bipyramidal structure, whereas the later, smaller lanthanide iodides LnI(3)(THF)(3.5) [Ln = Nd, Gd, Y] crystallize as solvent-separated ion pairs [LnI(2)(THF)(5)][LnI(4)(THF)(2)] in which the cations adopt a pentagonal bipyramidal geometry and the anions adopt an octahedral geometry in the solid state. 相似文献
8.
The pentafluorooxotellurate compound ReO(2)(OTeF(5))(3) has been synthesized from the reaction of ReO(2)F(3) with B(OTeF(5))(3) and structurally characterized in solution by (19)F and (125)Te NMR spectroscopy and in the solid state by Raman spectroscopy. The NMR and vibrational spectroscopic findings are consistent with a trigonal bipyramidal arrangement in which the oxygen atoms and an OTeF(5) group occupy the equatorial plane. The (19)F and (125)Te NMR spectra show that the axial and equatorial OTeF(5) groups of ReO(2)(OTeF(5))(3) are fluxional and are consistent with intramolecular exchange by means of a pseudorotation. The Lewis acid behavior of ReO(2)(OTeF(5))(3) is demonstrated by reaction with OTeF(5)(-). The resulting cis-ReO(2)(OTeF(5))(4)(-) anion was characterized as the tetramethylammonium salt in solution by (19)F and (125)Te NMR spectroscopy and in the solid state by Raman spectroscopy and X-ray crystallography. The compound crystallizes in the triclinic system, space group P&onemacr;, with a = 13.175(7) ?, b = 13.811(5) ?, c = 15.38(1) ?, alpha = 72.36(5)(o), beta = 68.17(5)(o), gamma = 84.05(4)(o), V = 2476(2) ?(3), D(calc) = 3.345 g cm(-)(3), Z = 4, R = 0.0547. The coordination sphere about Re(VII) in cis-ReO(2)(OTeF(5))(4)(-) is a pseudooctahedron in which the Re-O double bond oxygens are cis to one another. 相似文献
9.
The one-electron oxidized linear pentanuclear nickel complexes [Ni(5)(tpda)(4)(H(2)O)(BF(4))](BF(4))(2) (1) and [Ni(5)(tpda)(4)(SO(3)CF(3))(2)](SO(3)CF(3)) (2) have been synthesized by reacting the neutral compound [Ni(5)(tpda)(4)Cl(2)] with the corresponding silver salts. These compounds have been characterized by various spectroscopic techniques. Compound 1 crystallizes in the monoclinic space group P2(1)/n with a = 15.3022(1) A, b = 31.0705(3) A, c = 15.8109(2) A, beta = 92.2425(4) degrees, V = 7511.49(13) A(3), Z = 4, and compound 2 crystallizes in the monoclinic space group C2/c with a = 42.1894(7) A, b = 17.0770(3) A, c = 21.2117(4) A, beta = 102.5688(8) degrees, V = 14916.1(5) A(3), Z = 8. X-ray structural studies reveal an unsymmetrical Ni(5) unit for both compounds 1 and 2. Compounds 1 and 2 show stronger Ni-Ni interactions as compared to those of the neutral compounds. 相似文献
10.
Bumbu O Ceamanos C Crespo O Gimeno MC Laguna A Silvestru C Villacampa MD 《Inorganic chemistry》2007,46(26):11457-11460
The reaction of [AuCl(PR'3)] with KTeR, prepared from RTeTeR and K-selectride, gives the gold-tellurolate clusters [Au8(mu-TeR)8(PR'3)4] (R = Ph, Tol; PR'3 = PPh3, PPh2py) in high yield. This result contrasts with the one obtained from the reaction with thiolates or selenolates, from which mononuclear complexes are synthesized. The structures of these species have been determined and consist on three layers of gold and tellurium atoms in the ratio Au3Te2:Au2Te4:Au3Te2. There are short gold...gold interactions ranging from 2.9463(7) to 3.31132(7) A, and the clusters are composed of di- and tri-coordinated gold centers. The result is unprecedented in gold-chalcogenolate chemistry from which mononuclear species are expected and represents one of the few examples of gold-tellurolate derivatives. These species show an interesting luminescent behavior in the solid state (at 77 K) and in solution (both at 298 and 77 K). 相似文献
11.
X-ray crystal structures are reported for the following complexes: [Ru(2)Cl(3)(tacn)(2)](PF(6))(2).4H(2)O (tacn = 1,4,7-triazacyclononane), monoclinic P2(1)/n, Z = 4, a = 14.418(8) ?, b = 11.577(3) ?, c = 18.471(1) ?, beta = 91.08(5) degrees, V = 3082 ?(3), R(R(w)) = 0.039 (0.043) using 4067 unique data with I > 2.5sigma(I) at 293 K; [Ru(2)Br(3)(tacn)(2)](PF(6))(2).2H(2)O, monoclinic P2(1)/a, Z = 4, a = 13.638(4) ?, b = 12.283(4) ?, c = 18.679(6) ?, beta = 109.19(2) degrees, V = 3069.5 ?(3), R(R(w)) = 0.052 (0.054) using 3668 unique data with I > 2.5sigma(I) at 293 K; [Ru(2)I(3)(tacn)(2)](PF(6))(2), cubic P2(1)/3, Z = 3, a = 14.03(4) ?, beta = 90.0 degrees, V = 2763.1(1) ?(3), R (R(w)) = 0.022 (0.025) using 896 unique data with I > 2.5sigma(I) at 293 K. All of the cations have cofacial bioctahedral geometries, although [Ru(2)Cl(3)(tacn)(2)](PF(6))(2).4H(2)O, [Ru(2)Br(3)(tacn)(2)](PF(6))(2).2H(2)O, and [Ru(2)I(3)(tacn)(2)](PF(6))(2) are not isomorphous. Average bond lengths and angles for the cofacial bioctahedral cores, [N(3)Ru(&mgr;-X)(3)RuN(3)](2+), are compared to those for the analogous ammine complexes [Ru(2)Cl(3)(NH(3))(6)](BPh(4))(2) and [Ru(2)Br(3)(NH(3))(6)](ZnBr(4)). The Ru-Ru distances in the tacn complexes are longer than those in the equivalent ammine complexes, probably as a result of steric interactions. 相似文献
12.
Algarra AG Basallote MG Esther Castillo C Corao C Llusar R Jesús Fernández-Trujillo M Vicent C 《Dalton transactions (Cambridge, England : 2003)》2006,(48):5725-5733
The reaction of the incomplete-cuboidal [W(3)Se(4)(OH)(3)(dmpe)(3)](+) ([1](+)) cluster with acetic acid in acetonitrile solution leads to cluster fragmentation with formation of the dinuclear [W(2)Se(2)(mu-Se)(2)(mu-CH(3)CO(2))(dmpe)(2)](+) ([2](+)) complex. The X-ray structure of [2]PF(6) presents two equivalent metal centres bridged by one acetate ligand. Each W atom is additionally coordinated by one terminal selenium atom, two bridging selenido and two diphosphane phosphorus atoms in an essentially octahedral environment. Stopped-flow and conventional UV-vis studies indicate that fragmentation of [1](+) into [2](+) occurs through a complex mechanism. Three steps can be distinguished in the stopped-flow time scale, all of them showing a first order dependence with respect to the acetic acid concentration, followed by very slow spectral changes that lead to the formation of [2](+). Phosphorus NMR, electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (ESI-MS/MS) have been used to identify the nature of the reaction intermediates formed in the different steps. These studies indicate that the first two steps correspond to the formal substitutions of the hydroxo ligands at two metal centres by terminal acetate ligands. The third step involves bridging of one of the terminal acetate ligands, which actually prepares the trinuclear cluster to afford the acetate-bridged [W(2)Se(2)(mu-Se)(2)(mu-CH(3)CO(2))(dmpe)(2)](+) ([2](+)) complex. Although the precise details of the final conversion to [2](+) have not been established, the results obtained by combination of the different experimental techniques provide a complete picture of the speciation of the cluster [1](+) in acetonitrile solutions containing acetic acid. 相似文献
13.
Davies RP Giménez MA Patel L White AJ 《Dalton transactions (Cambridge, England : 2003)》2008,(42):5705-5707
The novel aluminium complexes [Al(2)(CyPS(3))(2)(CyPHS(2))(2)] and [Al(S(2)PPh(2))(3)] have been prepared as potential models for alumino-thiophosphonate based materials; [Al(2)(CyPS(3))(2)(CyPHS(2))(2)] is the first example of a primary dithiophosphinate to be characterised in the solid state. 相似文献
14.
15.
The reductant [Sm(N(SiMe(3))(2))(2)] was examined by cyclic voltammetry and UV-vis spectroscopy. Rate constants and activation parameters for the reduction of 1-iodobutane, 2-butanone, and methylacetoacetate by [Sm(N(SiMe(3))(2))(2)] were measured in THF by stopped-flow absorption decay experiments. Comparison with SmI(2) and SmI(2)-HMPA shows that the redox potential of [Sm(N(SiMe(3))(2))(2)] is intermediate between the SmI(2)-based reductants, yet it reduces alkyl iodides and ketones at a faster rate than the powerful combination of SmI(2) and HMPA. The activation data for reduction of alkyl iodides and ketones by [Sm(N(SiMe(3))(2))(2)] are consistent with highly ordered transition states having low activation barriers. All of these results taken together suggest that the mechanism of reduction of alkyl iodides and ketones by [Sm(N(SiMe(3))(2))(2)] has more inner-sphere character than reduction by SmI(2) or Sm-(HMPA) complexes. The change in the ET mechanism is attributed to the unique structure of the [Sm(N(SiMe(3))(2))(2)] complex. 相似文献
16.
The reaction of anhydrous YCl3 with an equimolar amount of lithium N,N'-diisopropyl-N' '-bis(trimethylsilyl)guanidinate, Li[(Me3Si)2NC(Ni-Pr)2], in tetrahydrofuran (THF) afforded the monomeric monoguanidinate dichloro complex {(Me3Si)2NC(Ni-Pr)2}YCl2(THF)2 (1). Alkylation of complex 1 with 2 equiv of LiCH2SiMe3 in hexane at 0 degrees C yielded the monomeric salt-free dialkyl complex {(Me3Si)2NC(Ni-Pr)2}Y(CH2SiMe3)2(THF)2 (2). The bis(triethylborohydride) complex [(Me3Si)2NC(Ni-Pr)2]Y[(mu-H)(mu-Et)2BEt]2(THF) (5) was prepared by the reaction of complex 1 with 2 equiv of LiBEt3H in a toluene-THF mixture at 0 degrees C. The complexes 1, 2, and 5 were structurally characterized. Complex 2 as well as the systems 2-Ph3B, 2-Ph3B-MAO, and 1-MAO (MAO = methylaluminoxanes) in toluene were inactive in ethylene polymerization, while the product obtained in situ from the reaction of complex 2 with a 2-fold molar excess of PhSiH3 in toluene polymerized ethylene with moderate activity. 相似文献
17.
The quadruply bonded metal-metal complexes cis-Mo(2)Cl(2)(6-mhp)(2)(PR(3))(2) (R(3) = Et(3), Me(3), Me(2)Ph, MePh(2); 6-mhp = 2-hydroxy-6-methylpyridinato) photoreact when their solutions are irradiated with visible and near-UV light. The primary photoprocess leads to the ligand redistribution products Mo(2)Cl(3)(6-mhp)(PR(3))(3) and Mo(2)Cl(6-mhp)(3)(PR(3)). In THF at room temperature, these photoproducts are stable and over time they back-react completely to the starting material. Photolysis of cis-Mo(2)Cl(2)(6-mhp)(2)(PR(3))(2) in DMF results in the same products; however, Mo(2)Cl(3)(6-mhp)(PR(3))(3) rapidly decomposes, leaving Mo(2)Cl(6-mhp)(3)(PR(3)) as the only isolable photoproduct. Conversely, when the reaction is carried out in benzene, Mo(2)Cl(6-mhp)(3)(PR(3)) undergoes a slow secondary photoreaction and Mo(2)Cl(3)(6-mhp)(PR(3))(3) is the photoproduct that is isolated. At a given wavelength, the photolysis quantum yield (Phi(p)) increases along the solvent series C(6)H(6) < THF < DMF (Phi(p)(405) = 0.00042, 0.00064, and 0.00097, respectively, for cis-Mo(2)Cl(2)(6-mhp)(2)(PMe(2)Ph)(2)). For a given solvent, Phi(p) increases with decreasing excitation wavelength (Phi(p)(546) = 0.00012, Phi(p)(436) = 0.00035, Phi(p)(405) = 0.00042, Phi(p)(366) = 0.0022, and Phi(p)(313) = 0.0079 in C(6)H(6)). This wavelength dependence of the photoreaction quantum yield in conjunction with the excitation spectrum establishes that the photoreaction does not originate from the lowest energy deltadelta excited state, which possesses a long lifetime and an appreciable emission quantum yield in C(6)H(6), CH(2)Cl(2), THF, and DMF. The photochemistry is instead derived from higher energy excited states with the maximum photoreactivity observed for excitation wavelengths coinciding with absorption features previously assigned to ligand-to-metal charge transfer transitions. 相似文献
18.
19.
Syntheses and Crystal Structures of the Rare-Earth Complexes [LaI2(THF)5]+I3?, [SmCl3(THF)4], [ErCl2(THF)5]+ [ErCl4(THF)2]?, [ErCl3(DME)2], and [Na(18-Crown-6)(THF)2]+[YbBr4(THF)2]? [LaI2(THF)5]+I3? ( 1 ) is obtained as red crystals from lanthanum powder and 1,2-diiodoethane in THF on exposure to light. Space group Pbcn, Z = 4, lattice dimensions at ?83°C: a = 1264.9, b = 2218.9, c = 1199.1 pm, R = 0.031. The lanthanum atom of the cation of 1 is coordinated with iodine atoms in the axial positions in a pentagonal-bipyramidal way. [SmCl3(THF)4] ( 2 ) originates as colourless crystals on heating SmCl3 with excess THF in the presence of Me3SiNPEt3. Space group P21/c, Z = 8, lattice dimensions at ?50°C: a = 3092.7, b = 826.2, c = 1758.3 pm, β = 93.85°, R = 0.054. Just like the known sample that crystallizes within the space group F2dd, 2 forms monomeric molecules in which the samarium atom is coordinated with two chlorine atoms in the axial positions in a distorted pentagonal-bipyramidal way. [ErCl2(THF)5]+[ErCl4(THF)2]? ( 3 ). Pale pink single crystals of 3 were prepared according to the described method by reaction of erbium powder with trimethylchlorosilane and methanol in THF. Space group C2/c, Z = 4, lattice dimensions at ?50°C: a = 1246.3, b = 1145.7, c = 2726.0 pm, β = 91.293°, R = 0.036. The erbium atom of the cation of 3 has a pentagonal-bipyramidal coordination with the chlorine atoms in the axial positions. Within the anion the THF molecules are in trans-arrangement of the octahedrally coordinated erbium atom. [ErC13(DME)2] ( 4 ) originates as pink single crystals from 3 with excess boiling 1,2-dimethoxyethane. Space group P21/c, Z = 4, lattice dimensions at ?50°C: a = 1137.2, b = 886.5, c = 1561.1 pm, β = 104.746°, R = 0.032. 4 forms monomeric molecules in which the erbium atom has a pentagonal-bipyramidal surrounding with two chlorine atoms in the axial positions. [Na(18-Krone-6)(THF)2]+ [YbBr4(THF)2]? ( 5 ) is formed as by-product by the reaction of YbBr3 with NaN(SiMe3)2 in THF in the presence-of 18-crown-6 forming colourless crystals. Space group P1 , Z = 1, lattice dimensions at ?70°C: a = 934.6, b = 988.9, c = 1208.0 pm, α = 73.82°, β = 72.98°, γ = 76.89°, R = 0.029. 5 contains isolated [YbBr4(THF)2]?ions, in which the THF molecules are arranged in trans-position. 相似文献
20.
The reactions of the molecular transition metal iodates A[CrO(3)(IO(3))] (A = K, Rb, Cs) with UO(3) under mild hydrothermal conditions provide access to four new, one-dimensional, uranyl chromatoiodates, Rb[UO(2)(CrO(4))(IO(3))(H(2)O)] (1) and A(2)[UO(2)(CrO(4))(IO(3))(2)] (A = K (2), Rb (3), Cs (4)). Under basic conditions, MoO(3), UO(3), and KIO(4) can be reacted to form K(2)[UO(2)(MoO(4))(IO(3))(2)] (5), which is isostructural with 2 and 3. The structure of 1 consists of one-dimensional[UO(2)(CrO(4))(IO(3))(H(2)O)](-) ribbons that contain uranyl moieties bound by bridging chromate and iodate anions as well as a terminal water molecule to create [UO(7)] pentagonal bipyramidal environments around the U(VI) centers. These ribbons are separated from one another by Rb(+) cations. When the iodate content is increased in the hydrothermal reactions, the terminal water molecule is replaced by a monodentate iodate anion to yield 2-4. These ribbons can be further modified by replacing tetrahedral chromate anions with MoO(4)(2)(-) anions to yield isostructural, one-dimensional [UO(2)(MoO(4))(IO(3))(2)](2)(-) ribbons. Crystallographic data: 1, triclinic, space group P(-)1, a = 7.3133(5) A, b = 8.0561(6) A, c = 8.4870(6) A, alpha = 88.740(1) degrees, beta = 87.075(1) degrees, gamma = 71.672(1) degrees, Z = 2; 2, monoclinic, space group P2(1)/c, a = 11.1337(5) A, b = 7.2884(4) A, c = 15.5661(7) A, beta = 107.977(1) degrees, Z = 4; 3, monoclinic, space group P2(1)/c, a = 11.3463(6) A, b = 7.3263(4) A, c = 15.9332(8) A, beta = 108.173(1) degrees, Z = 4; 4, monoclinic, space group P2(1)/n, a = 7.3929(5) A, b = 8.1346(6) A, c = 22.126(2) A, beta = 90.647(1) degrees, Z = 4; 5, monoclinic, space group P2(1)/c, a = 11.3717(6) A, b = 7.2903(4) A, c = 15.7122(8) A, beta = 108.167(1) degrees, Z = 4. 相似文献