Synthesis and Characterization of an Unexpected Asymmetric Binuclear Copper（Ⅰ） Complex Containing 4-Vinyl-pyridine

The asymmetric binuclear copper(I) complex [Cu₂(dppm)₂(C₇H₇N)(μ‐HCOO)](NO₃) (dppm=Ph₂PCH₂PPh₂, C₇H₇N=4‐vinyl‐pyridine) has been prepared and characterized by physicochemical and spectroscopic methods. The complex is photoluminescent at room temperature. It crystallizes in triclinic system, space group P‐1 with a= 1.2719(3) nm, b=1.8637(4) nm, c=1.1656(2) nm, a=97.16(3)°, β= 104.94(3)″, γ=89.39(3)°, V=2.648.1(9) nm³, D_c= 1.390 g.m^?3, Z=2, μ=0.974 mm^?1, R=0.0483 for 5716 independently observed reflections with I>2δ(I). The structure consists of [Cu₂(dppm)₂(C₇H₇N)(μ‐HCOO)]⁺cations and nitrate anions. The copper atoms show different coordination modes: Cu(1) displays a distorted trigonal and Cu(2) a tetrahedred geometry.     

Synthesis,X-ray structure and properties of the trinuclear copper(I) complex [Cu3(dppm)3(NO3)(OH)](NO3)

The novel trinuclear Cu^I complex [Cu₃(dppm)₃(NO₃)(OH)](NO₃) obtained by reacting dppm with Cu(NO₃)₂ · 3H₂O in the presence of NaBPh₄ was characterized by a single-crystal X-ray analysis as well as by physico-chemical and spectroscopic methods. The [Cu₃(dppm)₃(NO₃)(OH)]⁺ cation consists of a triangular array of copper atoms, (with dppm ligands bridging each edge of the triangle), a triply bridging OH group and NO^– ₃ anion bound to two faces of the Cu₃ unit, respectively.     

Novel Copper(I) Clusters with 2‐(Diphenylphosphanyl)anilide Ligands. Synthesis and Crystal Structures of [Cu6X2(NHR)4] (X = Cl,Br, I; R = C6H4‐2‐PPh2)

Treatment of copper(I) halides CuX (X = Cl, Br, I) with lithium 2‐(diphenylphosphanyl)anilide [Li(HL)] in THF led to the formation of hexanuclear copper(I) complexes [Cu₆X₂(HL)₄] [X = Cl ( 1 ), Br ( 2 ), I ( 3 )]. In compounds 1 – 3 , the copper atoms are in a distorted octahedral arrangement and the amide ligands adopt a μ₃‐κP,κ²N bridging mode. Additionally there are two μ₂‐bridging halide ligands. Each of the [Cu₆X₂(HL)₄] clusters comprises two copper atoms, which are surrounded by two amide nitrogen atoms in an almost linear coordination [Cu–N: 186.2(3)–188.0(3) pm] and four copper atoms, which are connected to an amide N atom, a P atom, and a halogen atom in a distorted trigonal planar fashion [Cu–N: 199.6(3)–202.3(3) pm)].     

π‐Complexes of Copper(I) with Terminal Alkynes. Synthesis and Crystal Structure of [(HC≡CCH2NH3)(Cu2Br3)] π‐Complex

Crystals of the zwitterionic copper(I) π‐complex [(HC≡CCH₂NH₃)Cu₂Br₃] have been synthesized by interaction of CuBr with [HC≡CCH₂NH₃]Br in aqueous solution (pH < 1) and X‐ray studied. The crystals are monoclinic: space group P2₁/n, a = 6.722(4), b = 12.818(8), c = 9.907(3) Å, β = 100.25(4)°, V = 840.0(8) ų, Z = 4, R = 0.0592 for 3015 reflections. The crystal structure of the π‐complex contains isolated [(HC≡CCH₂NH₃)⁺(Cu₂Br₃)^?]₂ units which are incorporated into a framework by strong hydrogen N–H···Br and C≡C–H···Br bonds. The length of π‐coordinated propargylammonium C≡C bond is equal 1.216(8) Å and Cu(I)–(C≡C) distance equals 1.958(5) Å.     

Konformation und Vernetzung von (CuCN)6‐Ringen in polymeren Cyanocupraten(I) [Cu2(CN)3—] (n = 2, 3)

Conformation and Cross Linking of (CuCN)₆‐Rings in Polymeric Cyanocuprates(I) equation/tex2gif-stack-8.gif [Cu₂(CN)₃^—] (n = 2, 3) The alkaline‐tricyano‐dicuprates(I) Rbequation/tex2gif-stack-9.gif[Cu₂(CN)₃] · H₂O ( 1 ) and Csequation/tex2gif-stack-10.gif[Cu₂(CN)₃] · H₂O ( 2 ) were synthesized by hydrothermal reaction of CuCN and RbCN or CsCN. The dialkylammonium‐tricyano‐dicuprates(I) [NH₂(Me)₂]equation/tex2gif-stack-11.gif[Cu₂(CN)₃] ( 3 ), [NH₂(iPr)₂]equation/tex2gif-stack-12.gif[Cu₂(CN)₃] ( 4 ), [NH₂(Pr)₂]equation/tex2gif-stack-13.gif[Cu₂(CN)₃] ( 5 ) and [NH₂(secBu)₂]equation/tex2gif-stack-14.gif[Cu₂(CN)₃] ( 6 ) were obtained by the reaction of dimethylamine, diisopropylamine, dipropylamine or di‐sec‐butylamine with CuCN and NaCN in the presence of formic acid. The crystal structures of these compounds are built up by (CuCN)₆‐rings with varying conformations, which are connected to layers ( 1 ) or three‐dimensional zeolite type cyanocuprate(I) frameworks, depending on the size and shape of the cations ( 2 to 6 ). Crystal structure data: 1 , monoclinic, P2₁/c, a = 12.021(3)Å, b = 8.396(2)Å, c = 7.483(2)Å, β = 95.853(5)°, V = 751.4(3)ų, Z = 4, d_c = 2.728 gcm^—1, R₁ = 0.036; 2 , orthorhombic, Pbca, a = 8.760(2)Å, b = 6.781(2)Å, c = 27.113(5)Å, V = 1610.5(5)ų, Z = 8, d_c = 2.937 gcm^—1, R₁ = 0.028; 3 , orthorhombic, Pna2₁, a = 13.504(3)Å, b = 7.445(2)Å, c = 8.206(2)Å, V = 825.0(3)ų, Z = 4, d_c = 2.023 gcm^—1, R₁ = 0.022; 4 , orthorhombic, Pbca, a = 12.848(6)Å, b = 13.370(7)Å, c = 13.967(7)Å, V = 2399(2)ų, Z = 8, d_c = 1.702 gcm^—1, R₁ = 0.022; 5 , monoclinic, P2₁/n, a = 8.079(3)Å, b = 14.550(5)Å, c = 11.012(4)Å, β = 99.282(8)°, V = 1277.6(8)ų, Z = 4, d_c = 1.598 gcm^—1, R₁ = 0.039; 6 , monoclinic, P2₁/c, a = 16.215(4)Å, b = 13.977(4)Å, c = 14.176(4)Å, β = 114.555(5)°, V = 2922(2)ų, Z = 8, d_c = 1.525 gcm^—1, R₁ = 0.070.     

Synthesis,characterization, and biological activity of a Cu(I) complex with 2-(9H-carbazol-9-yl) acetic acid

A new dicopper(I) complex with 2-(9H-carbazol-9-yl) acetic acid (HL) of the formula [Cu₂(dppm)₂L(NO₃)(CH₃OH)] [dppm = bis(diphenylphosphino)methane] was prepared. The complex was structurally characterized by IR, ¹H NMR spectra, and elemental analysis. Single crystal X-ray crystallography revealed that this complex is monoclinic, space group P2₁/c, with a = 13.6552(17) Å, b = 23.123(2) Å, c = 19.257(2) Å, α = γ = 90.00°, β = 106.860(2)°, V = 5818.8(11) ų, Z = 4, D _Calcd = 1.386 mg m^?3, F(000) = 2512, goodness-of-fit = 1.015. The complex was also tested in vitro for its cytotoxic activity using human hepatocellular carcinoma cell line (BEL-7402) and human hepatocellular liver carcinoma cell line (Hep-G2); 5-Fluorouracil was used as a positive control substance. The results indicated that the complex exhibited good cytotoxic activity against both human tumor cell lines.     

Copper(I) complexes of neutral,deprotonated and protonated 4,6-dimethylpyrimidine-2 (1H)-thione

Summary The following copper(I) complexes of 4,6-dimethylpyrimidine-2(1H)-thione (HL), its protonated cation (H₂L⁺) and deprotonated anion (L^–) have been prepared: CuL, Cu(HL)X (X = Cl, Br or I), Cu(HL)₂X (X = C1 or Br), Cu₂(HL)₃Br₂, Cu(H₂L)X₂ (X = Cl or Br), Cu₃(HL)₂LA₂ (A = ClO₄ or BF₄ ). The i.r. spectra show that in all the HL and L^– complexes and in the Cu(H₂L)Br₂ complex, the ligands are S, N coordinated to the metal ion, while in Cu(H₂L)Cl₂ only the thiocarbonylic sulphur is coordinated, probably bridging two copper(I) atoms. Thev(CuN) (288–317 cm^–1 ) andv(CuS) (191–225 cm^–1 ) have uniform frequency values in all the complexes. The halide ions are, in all their complexes, wholly or in part coordinated giving twov(CuX) bands which may indicate an asymmetrical Cu-X Cu halide bridging bond.Author to whom all correspondence should be directed.     

Halide Abstraction from Organic Solvents in Reactions of a Copper(I) Alkoxide: Synthesis and Crystal Structures of [Cu5(dppm)(dppm−)2(OtBu)Cl2] and [Cu3(dppm)3Br2][CuBr2]

The synthesis and structures of the two Cu^I halide complexes [Cu₅(dppm)(dppm^?)₂(O^tBu)Cl₂] and [Cu₃(dppm)₃Br₂][CuBr₂] (dppm = Ph₂PCH₂PPh₂, dppm^? = [Ph₂PCHPPh₂]^?) are reported. The compounds were obtained by treating reaction mixtures of [CuO^tBu] and dppm with dichloromethane or dibromomethane.     

Binuclear Copper(II) Complexes with Robsori-Type Ligands. Synthesis,characterization, crystal structure,and magnetic properties

Three binuclear copper(II) complexes, [Cu₂(μ-L)(μ-N₃)](ClO₄)2′ 1-5 EtOH (1), [Cu₂(μ-L)(μ-MeO)(ClO₄)]-ClO₄ - EtOH ( 2 ) and [Cu₂(μ-L)(μ-C₃H₃N₂)](ClO₄)₂ · 2H₂O, ( 3 ) where L is the pentadentale bridging ligand derived from 5-(tert-butyl)-2-hydroxybenzene-1, 3-dicarbaldehyde bis(benzoylhydrazone) ( HL ) were synthesized and characterized. The crystal-structure determination of complex 2 provided the following crystal data: monoclinic, space group P2₁}/a, a = 11.412(2), b = 24.509(4), c = 14.833(4) Å, β = 104.41(2)°, K = 4018(3) ų, Z = 4. The structure shows that the Cu^II ions are bridged by the endogenous phenolato O-atom and by an exogenous bridge CH₃O^?. The analysis of variable-temperature magnetic susceptibility data (4-300 K.) indicates that there is an antiferromagnetic interaction between the Cu^II ions in these complexes with an exchange parameter (2J) of ?119.1 cm^?1 for complex 1 and ?361.8 cm^?1 for complex 3 . The effect of some exogenous bridging ligands on magnetic coupling for this type of complex is suggested.     

Complexation of the 2, 4, 6‐Triallyloxy‐1, 3, 5‐triazine with Copper(I,II) Chlorides. Syntheses and Crystal Structures of [CuCl2·2C3N3(OC3H5)3], [Cu7Cl8·2C3N3(OC3H5)3], and [Cu8Cl8·2C3N3(OC3H5)3]·2C2H5OH

Interaction of copper(II) chloride with 2, 4, 6‐triallyloxy‐1, 3, 5‐triazine leads to formation of copper(II) complex [CuCl₂·2C₃N₃(OC₃H₅)₃] ( I ). Electrochemical reduction of I produces the mixed‐valence Cu^{I, II} π, σ‐complex of [Cu₇Cl₈·2C₃N₃(OC₃H₅)₃] ( II ). Final reduction produces [Cu₈Cl₈·2C₃N₃(OC₃H₅)₃]·2C₂H₅OH copper(I) π‐complex ( III ). Low‐temperature X‐ray structure investigation of all three compounds has been performed: I : space group P1¯, a = 8.9565(6), b = 9.0114(6), c = 9.7291(7) Å, α = 64.873(7), β = 80.661(6), γ = 89.131(6)°, V = 700.2(2) ų, Z = 1, R = 0.0302 for 2893 reflections. II : space group P1¯, a = 11.698(2), b = 11.162(1), c = 8.106(1) Å, α = 93.635(9), β = 84.24(1), γ = 89.395(8)°, V = 962.0(5) ų, Z = 1, R = 0.0465 for 6111 reflections. III : space group P1¯, a = 8.7853(9), b = 10.3602(9), c = 12.851(1) Å, α = 99.351(8), β = 105.516(9), γ = 89.395(8), V = 1111.4(4) ų, Z = 1, R = 0.0454 for 4470 reflections. Structure of I contains isolated [CuCl₂·2C₃N₃(OC₃H₅)₃] units. The isolated fragment of I fulfils in the structure of II bridging function connecting two hexagonal prismatic‐like cores Cu₆Cl₆, whereas isolated Cu₆Cl₆(CuCl)₂ prismatic derivative appears in III . Coordination behaviour of the 2, 4, 6‐triallyloxy‐1, 3, 5‐triazine moiety is different in all the compounds. In I ligand moiety binds to the only copper(II) atom through the nitrogen atom of the triazine ring. In II ligand is coordinated to the Cu^II‐atom through the N atom and to two Cu^I ones through the two allylic groups. In III all allylic groups and nitrogen atom are coordinated by four metal centers. The presence of three allyl arms promotes an acting in II and III structures the bridging function of the ligand moiety. On the other hand, space separation of allyl groups enables a formation of large complicated inorganic clusters.     

Synthesis,Structures, and Photophysics of Polynuclear Silver(I) Thiolate and Silver(I) Thiocarboxylate Complexes with Dppm Ligands

Trinuclear silver(I) thiolate and silver(I) thiocarboxylate complexes [Ag₃(μ‐dppm)₃(μ_n‐SR)₂](ClO₄) [n = 2, R = C₆H₄Cl‐4 ( 1 ) and C{O}Ph ( 2 ); n = 3, R = tBu ( 3 )], pentanuclear silver(I) thiolate complex [Ag₅(μ‐dppm)₄(μ₃‐SC₆H₄NO₂‐4)₄](PF₆) ( 4 ), and hexanuclear silver(I) thiolate complexes [Ag₆(μ‐dppm)₄(μ₃‐SR)₄]Y₂ [Y = ClO₄, R =C₆H₄CH₃‐4 ( 5 ) and C₁₀H₇ (2‐naphthyl) ( 7 ); Y = PF₆, R = C₆H₄OCH₃‐4( 6 )], were synthesized [dppm = bis(diphenylphosphanyl)methane] and their crystal structures as well as photophysical properties were studied. In the solid state at 77 K, trinuclear silver(I) thiolate and silver(I) thiocarboxylate complexes 1 and 2 exhibit luminescence at 470–523 nm, tentatively attributed to originate from the ³IL (intraligand) of thiolate or thiocarboxylate ligands, whereas hexanuclaer silver(I) thiolate complexes 5 and 7 produce dual emission, in which high‐energy emission is tentatively attributed to come from the ³IL of thiolate ligands and low‐energy emission is tentatively assigned to come from the admixture of metal ··· metal bond‐to‐ligand charge‐transfer (MMLCT) and metal‐centered (MC) excited states.     

Crystal structure of the reaction product of copper(II) nitrate with α-(3,3-Dimethyl-3,4-dihydro-1-isoquinolyl)hydroxy-iminoacetonitrile [Cu3(μ3-OH)(μ-L)3(NO3)2(H2O)] · 2H2O

The coordination compound [Cu₃(μ₃-OH)(μ-L)₃(NO₃)₂(H₂O)] · 2H₂O (I), where L is the α-(3,3-dimethyl-3,4-dihydro-1-isoquinolyl)hydroxyiminoacetonitrile anion, has been synthesized. The crystal and molecular structure of I was determined by X-ray diffraction (Enraf-Nonius CAD4, MoK _α radiation, graphite monochromator, ω-scan mode, 2θ_max = 49.96°, 7673 unique reflections, a = 12.745(3) ?, b = 13.726(3) ?, c = 28.835(6) ?, β = 93.44(3)°, V = 5035.2(17) ?³, Z = 4, space group P2₁/c). In the trimer complex I, the copper atoms are combined by a bridging hydroxy group. The copper atoms are additionally linked pairswise by three tridentate chelating bridging organic anions coordinated to the Cu(II) atoms by the N and O atoms of the deprotonated oxime group and by the N atom of the dihydroisoquinoline moiety. Original Russian Text ? V.I. Sokol, V.V. Davydov, N. Yu. Merkur’eva, E.I. Polyakova, Yu.V. Shklyaev, V.S. Sergienko, 2007, published in Zhurnal Neorganicheskoi Khimii, 2007, Vol. 52, No. 10, pp. 1643–1652.     

Synthesis and crystal structure of [Cu3(μ3-η1-CCPh)(μ-dppm)3][BF4]2, a tricopper(I) complex containing a μ3-η1 acetylide group and three bis(diphenylphosphino)methane (dppm) bridging ligands

The synthesis of the cationic trinuclear copper(I) complex [Cu₃(CCPh)(dppm)₃][BF₄]₂ is described. An X-ray structure determination shows a triangular array of copper atoms with three diphosphine ligands Ph₂PCH₂PPh₂ (dppm) bridging each edge of the triangle and a μ₃-η¹ phenyl acetylide group bound to the Cu₃ unit.     

Synthese und Strukturen neuer selenido‐ und selenolatoverbrückter Kupfercluster: [Cu38Se13(SePh)12(dppb)6] (1), [Cu(dppp)2][Cu25Se4(SePh)18(dppp)2] (2), [Cu36Se5(SePh)26(dppa)4] (3), [Cu58Se16(SePh)24(dppa)6] (4) und [Cu3(SeMes)3(dppm)] (5)

Syntheses and Crystal Structures of new Selenido‐ and Selenolato‐bridged Copper Clusters: [Cu₃₈Se₁₃(SePh)₁₂(dppb)₆] (1), [Cu(dppp)₂][Cu₂₅Se₄(SePh)₁₈(dppp)₂] (2), [Cu₃₆Se₅(SePh)₂₆(dppa)₄] (3), [Cu₅₈Se₁₆(SePh)₂₄(dppa)₆] (4), and [Cu₃(SeMes)₃(dppm)] (5) The reactions of copper(I) chloride or copper(I) acetate with monodentate phosphine ligands (PR₃; R = organic group) and Se(SiMe₃)₂ have already lead to the formation of CuSe clusters with up to 146 copper and 73 selenium atoms. If the starting materials and the bidentate phosphine ligands (Ph₂P–(CH₂)_n–PPh₂, n = 1: dppm, n = 3: dppp, n = 4: dppb; Ph₂P–C≡C–PPh₂: dppa) and silylated chalcogen derivates are changed (RSeSiMe₃; R = Ph, Mes) a series of new CuSe clusters can be synthesized. From single crystal X‐ray structure analysis one can characterise [Cu₃₈Se₁₃(SePh)₁₂(dppb)₆] ( 1 ), [Cu(dppp)₂] · [Cu₂₅Se₄(SePh)₁₈(dppp)₂] ( 2 ), [Cu₃₆Se₅(SePh)₂₆(dppa)₄] ( 3 ), [Cu₅₈Se₁₆(SePh)₂₄(dppa)₆] ( 4 ) and [Cu₃(SeMes)₃(dppm)] ( 5 ). In this new class of CuSe clusters, compounds 1 and 4 possess a spherical cluster skeleton, wheras 2 and 3 have a layered cluster core.     

Synthesis and Structural Characterization of Six Pentanuclear and Tetranuclear Mo/W‐Cu‐S Clusters with Bis(diphenylphosphanyl) Methane

Six heterothiometalic clusters, namely, [WS₄Cu₄(dppm)₄](ClO₄)₂ · 2DMF · MeCN ( 1 ), [MoS₄Cu₄(dppm)₄](NO₃)₂ · MeCN ( 2 ) [MoS₄Cu₃(dppm)₃](ClO₄) · 4H₂O ( 3 ), [WS₄Cu₃(dppm)₃](NO₃) · 4H₂O ( 4 ), [WS₄Cu₃(dppm)₃]SCN · CH₂Cl₂ ( 5 ), and [WS₄Cu₃(dppm)₃]I · CH₂Cl₂ ( 6 ) [dppm = bis (diphenylphosphanyl)methane] were synthesized. Compounds 1 – 4 were obtained by the reactions of (NH₄)₂MS₄ (M = Mo, W) with [Cu₂(μ₂‐dppm)₂(MeCN)₂(ClO₄)₂] {or [Cu(dppm)(NO₃)]₂} in the presence of 1,10‐phen in mixed solvent (CH₃CN/CH₂Cl₂/DMF for 1 and 2 , CH₂Cl₂/CH₃OH/DMF for 3 and 4 . Compounds 5 and 6 were obtained by one‐pot reactions of (NH₄)₂WS₄ with dppm and CuSCN (or CuI) in CH₂Cl₂/CH₃OH. These clusters were characterized by single‐crystal X‐ray diffraction as well as IR, ¹H NMR, and ³¹P NMR spectroscopy. Structure analysis showed that compounds 1 and 2 are “saddle‐shaped” pentanuclear cationic clusters, whereas compounds 3 – 6 are “flywheel‐shaped” tetranuclear cationic clusters. In 1 and 2 , the MS₄^2– unit (M = W, Mo) is coordinated by four copper atoms, which are further bridged by four dppm molecules. In compounds 3 – 6 , the MS₄^2– unit is coordinated by three copper atoms and each copper atom is bridged by three dppm ligands.     

Carbonylcobalt(I) complexes. The crystal and molecular structure of [Co(CO)(dppm)2]ClO4

New anionic carbonylcobalt(I) complexes [X₂Co(CO)₂(PPh₃)](PR₄) (X=Cl, PR₄ = PBzPh₃ (I); X = Br, PR₄ = PEtPh₃ (II)) have been prepared by reduction of the cobalt(II) halides with NaBH₄ in the presence of PPh₃ and the phosphonium salt PR₄X. Cleavage of halide bridges in dimeric or polymeric [XCo(PPh₃)₂]_n and [XCo(PPh₃)]_n gives the neutral dicarbonyl derivatives XCo(CO)₂PPh₃)₂. Treatment of ClCo(CO)₂(PPh₃)₂ with alkylating agents gives the known σ- and η- organocobalt(I) derivatives, and reactions with TIClO₄ in the presence of various amounts of different mono- and bi-dentate phosphines give the cationic tricarbonyl [Co(CO)₃(PPh₃)₂]⁺, dicarbonyl [Co(CO)₂(PMePh₂)₃]⁺ and monocarbonyl [Co(CO)L₄]⁺ complexes (L₄ = 4P(OMe)₃, 2 dppe and 2dppm). The dppm complex crystallizes in the monoclinic space group P2₁/c with a 17.895(6), b 10.751(2), c 24.687(4) Å, β 98.92(1)°, and D_calc 1.35 g cm⁻³ for Z = 4. A final R value of 0.077 ( R_w = 0.061), based on 2656 observed reflections, was obtained. The cobalt atom exhibits a distorted trigonal bipyramidal geometry. The perchlorate anion is severely disordered or freely rotating.     

Studies on solid state reactions of coordination compounds. XLVII. Solid state syntheses and crystal structures of cluster compounds {Cu3MoS3I} (PPh3)3S and {Cu3WS3Br} (PPh3)3S

Reactions of [NH⁴]₂[MS₄](M = Mo,W), CuX(X = Br, I) and PPh₃ in the solid state produced four mixed-metal sulfur containing clusters {Cu₃MS₃X}(PPh₃)₃S(M = Mo, W; X = Br, I), two of which (1: M = Mo, X = I; 2: M = W, X = Br) were structurally determined. Crystals of 1 and 2 are triclinic, space group P1 (1: a = 11.895(3), b = 13.107(1), c = 20.473(2)Å, α = 74.95(6), β = 84.87(8), γ = 64.27(7)°, Z=2, V=2776.1 ų, R_w = 0.064 for 6443 observed reflections. 2: a = 11.876 (1), b = 13.065 (2), c = 20.325(2)Å, α = 74.95(1), β= 85.39(1), γ = 64.09(1)°, Z = 2, V = 2737.3ų, R_w = 0.055 for ·5303 observed reflections). The results of the structure determination showed that the central units of the two cubane-like cluster compounds are composed of four metal atoms and four non-metal atoms situated at alternate corners. The differences of cubane-like cluster compounds obtained from solid state reactions and from solution reactions are discussed.     

Preparation, Crystal Structure and Properties of a Pentametallic 3-Ferrocenyl-2-crotonic acid-Bridged Copper（Ⅱ） Complex

The synthesis and characterization of the copper (II) complex [Cu₂(OOCCH = C(CH₃)Fc)₃(phen)₂]CIO₄ · 2H₂O (1) are reported. The structure of the complex was determined by single‐crystal X‐ray analysis. The compound crystallizes in the monoclinic system, space group Pc, with Z =2, a = 1.2799(4) nm, b =0.9969 (4) nm, c = 2.5228 nm, and β = 91.576 (1) °. The cationic part of 1 indicates a penametallic core in which three 3‐ferrocenyl‐2‐crotonic acid salt (FCA) groups act as (O, O') bridging ligands between two copper (II) ions with a square‐pyramidal environment. Cyclic voltammetric experiments in acetonitrile have been performed mainly to examine the Fe(II) → Fe(III) one‐electron oxidation in FCA and its complex. The variable‐temperature magnetic susceptibility measurements revealed very weak intramolecular anti‐ferromagnetic coupling. Fitting parameters are 2J = ‐0.2 cm^?1, g = 2.114, and θ = 0K.     

Crystallographic and spectroscopic studies of a luminescent binuclear copper(I) complex containing mixed-ligands

The luminescent binuclear copper(I) complex [Cu(dppm)(phen)]₂(NO₃)₂ · 6H₂O (dppm = Ph₂PCH₂PPh₂, phen = 1,10-phenanthroline) has been prepared and characterized by physicochemical and spectroscopic methods. The complex is photoluminescent at room temperature. Its X-ray crystal structure shows that dppm coordinates as a bridging ligand, and phen as a bidentate ligand to the copper(I) atoms of the tetrahedral structure.