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1.
The reaction of the bisguanidine copper(I) compounds [Cu(btmgp)I] and [Cu2(btmgp)2][PF6]2 with molecular oxygen afforded at low temperatures complexes containing the bis-μ-oxo dicopper(III) core, which is capable to hydroxylate one of the N-CH3-groups of the {bis(tetramethyl)guanidino}propane ligands. The formation of the novel ligand {bis(trimethylmethoxy)guanidino}propane (btmmO) is reported as it represents the first hydroxylation of a N-methyl group. The products of this reaction are novel alkoxo-bridged binuclear copper complexes, namely [Cu2(btmmO)2I]+ containing an iodide ion in a novel bridging situation, as well as [Cu2(btmmO)2]2+ which have been identified in their complex salts and [Cu2(btmmO)2][PF6]2 · 2MeCN, respectively. Concomitantly, the hydroxo-bridged binuclear copper compounds [Cu2(btmgp)2(μ-OH)2]I2 and [Cu2(btmgp)2(μ-OH)2][PF6]2 are formed as couple products. The formation of the bis-μ-oxodicopper(III) complexes was monitored by UV/Vis-spectroscopy, and the reaction products were characterised by X-ray diffraction, vibrational spectroscopy and elemental analysis.  相似文献   

2.
The binuclear mixed valence copper(I/II) compound [CuI(CN)3CuII(tn)2] (1) (tn = propane-1,3-diamine) and its acetonitrile adduct [CuI(CN)3CuII(tn)2] · 2MeCN (2) have been synthesized. Complex 1 crystallizes triclinic, space group , a = 8.117(2) Å, b = 8.389(2) Å, c = 11.920(2) Å, α = 108.728(3)°, β = 100.024(3)°, γ = 104.888(4)°, Z = 2, and compound 2 monoclinic, space group P21/m, a = 8.752(2) Å, b = 13.243(3) Å, c = 9.549(2) Å, β = 114.678(4)°, Z = 2. In both crystal structures, the binuclear [CuI(CN)3CuII(tn)2] complex with slightly different bonding geometries is formed. One of the three nitrogen atoms of a CuI(CN)3 moiety is coordinated to Cu(II) at the apex of a square-pyramid with two chelating ligands tn on its base. The shortest intramolecular CuII?CuII distance in 1 is 5.640(7) Å. The EPR behaviour of 1 has been investigated at room temperature and at 77 K. The magnetic properties were measured in the temperature range 1.8-300 K.  相似文献   

3.
Two alternating 1-D metal-radical linear [L:Cu(hfac)2]n and zig-zag [L:Mn(hfac)2]n chains (where L = 4-trimethylsilylethynyl-1-(4,4,5,5-tetramethyl-3-oxylimidazoline-1-oxide)benzene) and hfac = hexafluoroacetylacetonate) are described and characterized by X-ray diffraction of their crystals. Bulk magnetic measurements of L:Cu(hfac)2 indicated a ferromagnetic interaction with J = 6 cm−1 and L:Mn(hfac)2 yielded ferrimagnetic interactions with J = −95 cm−1. For the latter, a strong increase of their magnetic moment at lowest temperatures was observed only at very low static magnetic field, while for Hdc > 0.05 T saturation effect led to a downward slope after reaching a maximum.  相似文献   

4.
The reactions of the Keplerate super cluster [Mo132O372(CH3CO2)30(H2O)72]42− with a Cu(II) source and an organonitrogen donor in methanol/DMF solutions yielded a series of bimetallic organic-inorganic oxide hybrid materials, including the molecular species [Cu(phen)2MoO4] (1) and [{Cu(terpy)}2(MoO4)2] (2) and a series of materials constructed from the tetranuclear building block {Mo4O10(OMe)6}2−: the molecular [{Cu2(phen)2(O2CCH3)2 (MeOH)}Mo4O10(OMe)6] (3), [{Cu(terpy)(O2CCH3)}2Mo4O10(OMe)6] (4) and [{Cu(terpy)Cl}2Mo4O10(OMe)6] (5), the one-dimensional phases [{Cu(bpy)(HOMe)2}Mo4O10(OMe)6] (6), [{Cu(bpy)(DMF)2}Mo4O10(OMe)6] (7), [{Cu(bpa)(DMF)2}Mo4O10(OMe)6] (8), [{Cu(phen)(DMF)2}Mo4O10(OMe)6] (9) and [{CuCl(dpa)}2Mo4O10(OMe)6] (10), and the two-dimensional material [{Cu2(DMF)2(pdpa)}{Mo4O10(OMe)6}2] (11). When methanol is replaced by the tridentate alkoxide tris-methoxypropane (trisp), the {Mo2O4(trisp)2}2− cluster building block is observed for [Cu(phen)Mo2O4(trisp)2] (12), [Cu(bpa)(DMF)Mo2O4(trisp)2] (13) and [{Cu(bpy)(NO3)}2Mo2O4(trisp)2] (14).  相似文献   

5.
Dark-brown single crystals of the title compound 1 were obtained in high yield by layering a CuCl2 solution in 25% aqueous ammonia on a glycerol solution of K6[W4Te4(CN)12]·5H2O. The complex 1 was characterized by single crystal X-ray diffraction analysis and IR spectroscopy. The X-ray structure of 1 reveals a polymeric chain cyano-bridged cluster-metal coordination compound. The [W4Te4(CN)12]6− cluster anions are linked one to another by Cu2+ cations through coordination by nitrogen atoms of the CN groups.  相似文献   

6.
Two new heterometallic complexes, [Cu(en)(H2O)]2[Fe(CN)6]·4H2O (1) and [Cu(en)2][KFe(CN)6] (2), have been isolated from the reactions of CuCl2 and en with K3[Fe(CN)6] in different molar ratios. Both complexes have been characterized by X-ray analyses, IR spectra and elemental analyses. Complex 1 is a cyanide bridged bimetallic assembly, its crystal structure consists of a two-dimensional polymeric sheet with two different rings, one a four-membered square ring and another a 12-membered hexagonal ring. The Fe(II) ion of 1 has two terminal, two linear bridging and two 1,1 en-on bridging cyanide groups. In the crystal structure of 2, the neighboring [Fe(CN)6]3− units are bridged by the K+ and the [K[Fe(CN)6]]2− units forming a three-dimensional network structure. The [Cu(en)2]2+ units fill in the holes of the network acting as counter cations and charge compensations. Variable temperature magnetic susceptibility studies of 1 indicate that the complex exhibits ferromagnetic interaction between the Cu(II) ions.  相似文献   

7.
Reaction of Cu(ClO4)2·6H2O, SRaaiNR′ (1-alkyl-2-[(o-thioalkyl)phenylazo]imidazole) and NH4SCN (1:1:2 mol ratio) affords distorted square pyramidal, [CuII(SRaaiNR′)(SCN)2] (3) compound while identical reaction with [Cu(MeCN)4](ClO4) yields -SCN- bridged coordination polymer, [CuI(SRaaiNR′)(SCN)]n (4). These two redox states [CuII and CuI] are interconvertible; reduction of [CuII(SRaaiNR′)(SCN)2] by ascorbic acid yields [CuI(SRaaiNR′)(SCN)]n while the oxidation of [CuI(SRaaiNR′)(SCN)]n by H2O2 in presence of excess NH4SCN affords [CuII(SRaaiNR′)(SCN)2]. They are structurally confirmed by single crystal X-ray diffraction study. Cyclic voltammogram of the complexes show Cu(II)/Cu(I) redox couple at ∼0.4 V and azo reductions at negative to SCE. UV light irradiation in MeCN solution of [CuI(SRaaiNR′)(SCN)]n (4) show trans-to-cis isomerisation of coordinated azoimidazole. The reverse transformation, cis-to-trans, is very slow with visible light irradiation while the process is thermally accessible. Quantum yields (?t→c) of trans-to-cis isomerisation are calculated and free ligands show higher ? than their Cu(I) complexes. The activation energy (Ea) of cis-to-trans isomerisation is calculated by controlled temperature experiment. Copper(II) complexes, 3, do not show photochromism. DFT and TDDFT calculation of representative complexes have been used to determine the composition and energy of molecular levels and results have been used to explain the solution spectra, photochromism and redox properties of the complexes.  相似文献   

8.
Complexes of the type [Pt(amine)4]I2 were synthesized and characterized mainly by multinuclear (195Pt, 1H and 13C) magnetic resonance spectroscopy. The compounds were prepared with different primary amines, but not with bulky amines, due to steric hindrance. In 195Pt NMR, the signals were observed between −2715 and −2769 ppm in D2O. The coupling constant 3J(195Pt-1H) for the MeNH2 complex is 42 Hz. In 13C NMR, the average values of the coupling constants 2J(195Pt-13C) and 3J(195Pt-13C) are 18 and 30 Hz, respectively. The crystal structure of [Pt(EtNH2)4]I2 was determined by X-ray diffraction methods. The Pt atom is located on an inversion center. The structure is stabilized by H-bonding between the amines and the iodide ions. The compound with n-BuNH2 was found by crystallographic methods to be [Pt(n-BuNH2)4]2I3(n-BuNHCOO). The crystal contains two independent [Pt(CH3NH2)4]2+ cations, three iodide ions and a carbamate ion formed from the reaction of butylamine with CO2 from the air. When the compound [Pt(CH3NH2)4]I2 was dissolved in acetone, crystals identified as trans-[Pt(CH3NH2)2(H3CNC(CH3)2)2]I2 were isolated and characterized by crystallographic methods. Two trans bonded MeNH2 ligands had reacted with acetone to produce the two N-bonded Schiff base Pt(II) compound.  相似文献   

9.
The novel ferromagnetic coupling one-dimensional complex {Cu(NIT3Py)2[N(CN)2]2(H2O)2} (NIT3Py=2-(3-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) was synthesized and characterized structurally and magnetically. It crystallizes in the monoclinic space group C2/c. The Cu(II) ion is in a distorted octahedral environment. The units of {Cu(NIT3Py)2[N(CN)2]2(H2O)2} were connected as one-dimensional structure by the intermolecular hydrogen bonds. Magnetic measurements show that there are intramolecular ferromagnetic interactions and intermolecular antiferromagnetic interactions within the chain.  相似文献   

10.
Two novel bimetallic coordination polymers, [Cu(en)2][Mn(dca)4] (1) and [Cu(pn)2][Mn(dca)4] (2) (en, ethylenediamine; pn, 1,3-diaminopropane; dca, dicyanamide N(CN)2), have been synthesized and characterized. Both of them consist of Mndca anionic chains and chelate cations of copper. 1 has a sheet like architecture built by the [Cu(en)2]2+ cations and the homoleptic trans-[Mn(dca)4 2−]n chains. 2 shows unusual 3-D threefold interpenetrating diamond-like structure constructed by [Cu(pn)2]2+ cations and the homoleptic cis-[Mn(dca)4 2−]n chains. The magnetic susceptibilities obey the Curie-Weiss law with weak antiferromagnetic interactions.  相似文献   

11.
Reaction of [Rh(CO)2I]2 (1) with MeI in nitrile solvents gives the neutral acetyl complexes, [Rh(CO)(NCR)(COMe)I2]2 (R=Me, 3a; tBu, 3b; vinyl, 3c; allyl, 3d). Dimeric, iodide-bridged structures have been confirmed by X-ray crystallography for 3a and 3b. The complexes are centrosymmetric with approximate octahedral geometry about each Rh centre. The iodide bridges are asymmetric, with Rh-(μ-I) trans to acetyl longer than Rh-(μ-I) trans to terminal iodide. In coordinating solvents, 3a forms mononuclear complexes, [Rh(CO)(sol)2(COMe)I2] (sol=MeCN, MeOH). Complex 3a reacts with pyridine to give [Rh(CO)(py)(COMe)I2]2 and [Rh(CO)(py)2(COMe)I2] and with chelating diphosphines to give [Rh(Ph2P(CH2)nPPh2)(COMe)I2] (n=2, 3, 4). Addition of MeI to [Ir(CO)2(NCMe)I] is two orders of magnitude slower than to [Ir(CO)2I2]. A mechanism for the reaction of 1 with MeI in MeCN is proposed, involving initial bridge cleavage by solvent to give [Rh(CO)2(NCMe)I] and participation of the anion [Rh(CO)2I2] as a reactive intermediate. The possible role of neutral Rh(III) species in the mechanism of Rh-catalysed methanol carbonylation is discussed.  相似文献   

12.
The reactivity of the metalloligand [Pt2(μ-S)2(PPh3)4] towards a variety of indium(III) substrates has been explored. Reaction with excess In(NO3)3 and halide (KBr or NaI) gave the four-coordinate adducts [Pt2(μ-S)2(PPh3)4InX2]+[InX4] (X = Br, I). An X-ray structure determination on the iodo complex revealed a slightly distorted tetrahedral coordination geometry at indium. In contrast, reaction of [Pt2(μ-S)2(PPh3)4] with indium(III) chloride was more complex; the ion [Pt2(μ-S)2(PPh3)4InCl2]+ was initially observed in solution (using ESI mass spectrometry), and isolated as its BPh4 salt. Analysis of [Pt2(μ-S)2(PPh3)4InCl2]+[BPh4] by ESI MS showed the parent cation when analysed in MeCN solution. However in solutions containing methanol, partial solvolysis occurred to give the di-indium species [{Pt2(μ-S)2(PPh3)4InCl(OMe)}2]2+ (proposed to contain an In2(μ-OMe)2 unit with five-coordinate indium) and its fragment ion [Pt2(μ-S)2(PPh3)4InCl(OMe)]+. Reaction of [Pt2(μ-S)2(PPh3)4] with InCl3·3H2O, 8-hydroxyquinoline (HQ) and trimethylamine in methanol gave the adduct [Pt2(μ-S)2(PPh3)4InQ2]+, isolated as its PF6 salt. The same cationic complex is formed when [Pt2(μ-S)2(PPh3)4] is reacted with InQ3 in methanol, but in this case the product is contaminated with the mononuclear complex [(Ph3P)2PtQ]+ formed by disintegration of the trinuclear complex [Pt2(μ-S)2(PPh3)4InQ2]+ with byproduct Q. [(Ph3P)2PtQ]+BPh4 was independently prepared from cis-[PtCl2(PPh3)2] and HQ/Me3N, and is the first example of a platinum 8-hydroxyquinolinate complex containing phosphine ligands.  相似文献   

13.
The synthesis and structural characterization of the copper salts [Cu2(2-Boc-benzoate)4(dme)2] (1), [Cu(2-Boc-benzoate)2(tmeda)] (2), [Cu2(2-Boc-benzoate)2(dppm)] (3), [Cu(2-Boc-nicotinate)(PPh3)2] (4), [Cu2{2-Boc-5,6-anhydride-naphthylcarboxylate}2(dppm)2] (5) [dme = 1,2-dimethoxyethane, dppm = bis(diphenylphosphino)methane, tmeda = N,N′-tetramethylethylenediamine, Boc = tert-butoxycarbonyl] prove that cyclic organic anhydrides and dianhydrides readily insert into the Cu-O bond of [CuOtBu] forming carboxylate ligands with ester functionalities in the ligand periphery. [Sb(CO2Ph-o-CO2Me)2(OMe)(tmeda)] (6) was synthesised by insertion reaction of Sb(OMe)3 with phthalic anhydride.  相似文献   

14.
Salts of the Fe(III) spin crossover cation [FeIII(qsal)2]+ (qsalH = N-(8-quinolyl)salicylaldimine) and monoanions [MIII(pds)2] (M = Cu, Au; pds = pirazine-2,3-diselenolate) with formula [FeIII(qsal)2][MIII(pds)2] were prepared and characterized by single crystal X-ray diffraction and magnetic measurements. These two salts present magnetic properties essentially due to the FeIII centres in the high-spin state (S = 5/2), and do not have any spin transition.  相似文献   

15.
One-pot reactions of transition metal (CuII, NiII, CoII, or CdII) salt with malonic acid (H2mal) in the presence of mesocyclic diamine generate three supramolecular complexes and a coordination polymer. [Cu(mal)2(H2O)2](H2O)2(H2DACH) (1) and [M(mal)2(H2O)2](H2DACO) (M = Ni for 2, and Co for 3) are ion-pair products and managed by charge-assistant noncovalent interactions (DACO = 1,5-diazacyclooctane, and DACH = 1,4-diazacycloheptane). In these structures, the similar mononuclear [M(mal)2(H2O)2]2− building blocks are connected by hydrogen bonds to form 2D networks (with the aid of one lattice water in the case of 1), which are further extended by the cationic diamine components to yield 3D pillar-layered solids. While [Cd(mal)(H2O)2]n (4) is a neutral polymeric complex, in which the similar [Cd(mal)2(H2O)2]2− subunits are propagated by additional Cd-O coordinative forces to result in the final 2D layer.  相似文献   

16.
A series of luminescent tetranuclear cuboidal copper(I) diynyl complexes, [Cu4(PAr3)431-CCCCR′)4] (Ar=Ph, R′=Ph, C6H4CH3-p, C6H4OCH3-p; Ar=C6H4CH3-p, C6H4F-p, R′=Ph) has been synthesized and characterized. The X-ray crystal structure of [Cu4(PPh3)431-CCCCPh)4] has been determined. The origin of the low-energy emission in the complexes is assigned as derived from a metal-centered 3d94s1 state, mixed with LMCT [diynyl→Cu4] and IL [π-π*(diynyl)] states.  相似文献   

17.
The preparation, crystal structures and magnetic properties of three copper(II) compounds of formulae [Cu2(dmphen)2(dca)4] (1), [Cu(dmphen)(dca)(NO3)]n (2) and [Cu(4,4-dmbpy)(H2O)(dca)2] (3) (dmphen=2,9-dimethyl-1,10-phenanthroline, dca=dicyanamide and 4,4-dmbpy=4,4-dimethyl-2,2-bipyridine) are reported. The structure of 1 consists of discrete copper(II) dinuclear units with double end-to-end dca bridges whereas that of 2 is made up of neutral uniform copper(II) chains with a single symmetrical end-to-end dca bridge. Each copper atom in 1 and 2 is in a distorted square pyramidal environment: two (1) or one (2) nitrile-nitrogen atoms from bridging dca groups, one of the nitrogen atoms of the dmphen molecule (1 and 2) and either one nitrile-nitrogen from a terminal dca ligand (1) or a nitrate-oxygen atom (2) build the equatorial plane whereas the second nitrogen atom of the heterocyclic dmphen fills the axial position (1 and 2). The copper-copper separations through double (1) and single (2) end-to-end dca bridges are 7.1337(7) (1) and 7.6617(7) (2). Compound 3 is a mononuclear copper(II) complex whose structure contains two neutral and crystallographically independent [Cu(4,4-dmbpy)(H2O)(dca)2] molecules which are packed in two different layer arrangements running parallel to the bc-plane and alternating along the a-axis. The copper atoms in both molecules have slightly distorted square pyramidal surroundings with the two nitrogen atoms of the 4,4-dmbpy ligand and two dca nitrile-nitrogen atoms in the basal plane and a water oxygen in the apical position. A semi co-ordinated dca nitrile-nitrogen from a neighbour unit [2.952(6) Å for Cu(2)-N] is in trans position to the apical water molecule in one of the two molecules, this feature representing part of the difference in supramolecular connections in the alternating layers referred to above. Magnetic susceptibility measurements for 1-3 in the temperature range 1.9-290 K reveal the occurrence of weak antiferromagnetic interactions through double [J=−3.3 cm−1 (1), ] and single [J=−0.57 cm−1 (2), ] dca bridges and across intermolecular contacts [θ=−0.07 K (3)].  相似文献   

18.
New copper(II) complexes [CuL2]2+ (L2=7,7,9-trimethyl-1,3,6,10,13-pentaazabicyclo[11,2,11.13]hexadec-9-ene) and [Cu2(L3)(H2O)2]4+ have been prepared by the reaction of [CuL1]2+ (L1=5,5,7-trimethyl-1,4,8,11,14-pentaazatetradce-7-ene) and formaldehyde. The mononuclear complex [CuL2]2+ has a square-planar coordination geometry with a 5-6-5-6 chelate ring sequence and is relatively stable even in low pH at room temperature. The dinuclear complex [Cu2(L3)(H2O)2]4+ consists of two unsaturated 15-membered pentaaza macrocyclic units (7,7,9-trimethyl-1,3,6,10,13-pentaazacyclopentadec-9-ene) that are linked together by a methylene group in a tilted face-to-face arrangement [Cu?Cu distance: 7.413(2) Å ]. Each macrocyclic unit of [Cu2(L3)(H2O)2]4+ contains one four-membered chelate ring and has a severely distorted octahedral coordination polyhedron. The dinuclear complex is quite stable in aqueous solutions containing an excess of formaldehyde or in dry acetonitrile but is decomposed to [CuL1]2+ and [CuL2]2+ in pure water.  相似文献   

19.
A hexarhenium cyanohydroxo anionic cluster complex [Re6Se8(CN)4(OH)2]4− was synthesized for the first time starting from [Re6Se8(OH)6]4−, which was crystallized as a salt of the composition Cs2.75K1.25[Re6Se8(CN)4(OH)2]·H2O (1). The reaction of the complex with Cu2+ in an aqueous ammonia or methylamine solutions afforded [Cu(NH3)5]2[Re6Se8(CN)4(OH)2]·8H2O (2) or [{Cu(CH3NH2)4}2Re6Se8(CN)4(OH)2] (3), respectively. All of these three compounds were characterized by a single-crystal X-ray diffraction method. Compound 1 is crystallized in the tetragonal space group I4/m with eight formula units per cell (a = b = 17.4823(14) Å, c = 19.430(2) Å, V = 5938.3(10) Å3); compound 2 is crystallized in the monoclinic space group P21/n with two formula units per cell (a = 12.1845(13) Å, b = 8.6554(9) Å, c = 19.2568(19) Å, β = 91.081(2)°, V = 2030.5(4) Å3); compound 3 is crystallized in the orthorhombic space group Cmcm with four formula units per cell (a = 19.816(4) Å, b = 14.611(3) Å, c = 13.751(3) Å, V = 3981.2(13) Å3). The luminescence properties of 1 were studied in both aqueous solution and solid state. In addition, the electronic structure of [Re6Se8(CN)4(OH)2]4− was elucidated by DFT calculations.  相似文献   

20.
New copper(I) triorganophosphane derivatives [Cu(PR3)n{H2B(btz)2}] and [Cu(PR3)n{HB(btz)3}] (n=1 or 2) have been synthesized from the reaction of CuCl with PR3 (R=phenyl, cyclohexyl, benzyl, o-, m-, or p-tolyl) or PMePh2 and potassium dihydrobis(1,2,3-benzotriazolyl)borate K[H2B(btz)2] or potassium hydrotris(1,2,3-benzotriazolyl)borate K[HB(btz)3]. The complexes obtained have been characterized by elemental analyses and FT-IR in the solid state and by NMR (1H and 31P{1H}) spectroscopy and conductivity measurements in solution. Solution data are consistent with partial dissociation of complexes occurring throughout breaking of the CuP bond. Single crystal structural characterizations were undertaken for two of them. The structurally authenticated arrays are, (a) [Cu(PBn3)2{(btz)BH2(btz)}] with a three coordinate P2Cu(N) coordination sphere and the donor [H2B(btz)2] coordinated throughout only one N3 atom. (b) [Cu(P-m-tolyl3)n{(btz)3BH}] with a four coordinate PCuN3 coordination sphere with the tris(benzotriazolyl)borate acting as tripodal donor throughout all its N2 atoms.  相似文献   

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