Syntheses of Binuclear Copper(Ⅰ)Complexes Containing Benzimidazole

A binuclear copper(Ⅰ) complex [Cu2(dppm)2(C7H6N2)2](NO3)2 (C7H6N2 = benzimidazole, dppm = Ph2PCH2PPh2) has been synthesized and characterized by X-ray crystallography.The crystal belongs to monoclinic, space group C2/c with a = 14.167(3), b = 21.209(4), c =20.680(4) A, β = 103.93(3)°, C32H28CuN3O3P2, Mr = 628.05, Z = 8,μ = 0.868 mm-1, V = 6031 (2)(。A)3,F(000) = 2592, Dc= 1.383 g/cm3, R = 0.0593 and wR = 0.1736.A total of 5297 independent reflec tions were collected, of which 3503 were observed with I ＞ 2σ(I).The central copper atom is tri-coordinated by phosphorus atoms from bridging dppm and nitrogen atom from benzimidazole.In the coordination sphere, the bond lengths of Cu-P(1) and Cu-P(2) are 2.2607(17) and 2.2503(16)(。A),respectively and the P-Cu-P bond angle is 127.26(6)°.     

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

Introduction Many examples of complexes containing the eight-membered ring M(-dppm)M' are known with a variety of metals, oxidation states and stereochemis-tries.1-4 In general, they contain trans-bound, bridging dppm ligands to give a planar M2P4 core structure with the two metal atoms held in close proximity to each other (regardless of whether a metal-metal bond is pre-sent or not). This feature is presumably one of the chief reasons for the unusual bonding, reactivity and catalytic prope…     

Syntheses and Crystal Structures of Mono-and Binuclear Copper(Ⅱ) Mixed-ligand Complexes Involving Schiff Base

1 INTRODUCTION The chemistry of copper compounds has been extensively investigated and the relationship be- tween structure and reactivity, ranging from indus- trial catalysis to biochemistry activity, is of major importance. For binuclear copper(II) complexes equa- torially bridged by pair of hydroxide[1] or alkoxide[2, 3] groups, satisfactory linear correlation is found be- tween the Cu–O–Cu bridging angle and spin coupling between the metal centers. However, for binuclear copper(I…     

Synthesis and Crystal Structure of [Cu(phen)_2(SO_4)(H_2O)]·0.5C_4H_4O_4·7H_2O

1INTRODUCTION The construction of metal-organic coordination polymers based on covalent interactions[1]or supra-molecular contacts such as hydrogen-bonding and/orπ-πinteractions)[2]is now of great interest not only due to the enormous variety of intriguing structural topologies themselves,but also to their unexpected physical and chemical properties for potential prac-tical applications as functional materials.Many N-containing ligands,such as4,4?-bipyridine,2,2?-bi-pyridine and1,10-phen…     

Synthesis and Structure of bis(μ-2-aminopyridine N-oxide)-bis[dichlorocopper(II)]

1 INTRODUCTIONMany complexes of 2-aminopyridine N-oxide (apo) have been characterized by infrared spectra, X-ray powder diffraction spectra, and by magnetic measurements and electronic spectra at liquid nitrogen temperature, but very few of them are their crystal X-ray studies[1~3]. Recently, a number of bridged binuclear copper (II) complexes have been reported, some of which have important potential applications in bioinorganic chemistry and materials[4~6]. Particularly, the complexes …     

Synthesis of 1D {Cu6(mu3-SC3H6N2)4(mu-SC3H6N2)2(mu-I)2I4}n and 3D {Cu2(mu-SC3H6N2)2(mu-SCN)2}n polymers with 1,3-imidazolidine-2-thione: bond isomerism in polymers

The reaction of copper(I) iodide with 1, 3-imidazolidine-2-thione (SC3H6N2) in a 1:2 molar ratio (M/L) has formed unusual 1D polymers, {Cu6(mu3-SC3H6N2)4(mu-SC3H6N2)2(mu-I)2I4}n (1) and {Cu6(mu3-SC3H6N2)2(mu-SC3H6N2)4(mu-I)4I2}n (1a). A similar reaction with copper(I) bromide has formed a polymer {Cu6(mu3-SC3H6N2)2(mu-SC3H6N2)4(mu-Br)4Br2}n (3a), similar to 1a, along with a dimer, {Cu2(mu-SC3H6N2)2(eta1-SC3H6N2)2Br2} (3). Copper(I) chloride behaved differently, and only an unsymmetrical dimer, {Cu2(mu-SC3H6N2)(eta1-SC3H6N2)3Cl2} (4), was formed. Finally, reactions of copper(I) thiocyanate in 1:1 or 1:2 molar ratios yielded a 3D polymer, {Cu2(mu-SC3H6N2)2(mu-SCN)2}n (2). Crystal data: 1, C9H18Cu3I3N6S3, triclinic, P, a = 9.6646(11) A, b = 10.5520(13) A, c = 12.6177(15) A, alpha = 107.239(2) degrees , beta = 99.844(2) degrees , gamma = 113.682(2) degrees , V = 1061.8(2) A(3), Z = 2, R = 0.0333; 2, C(4)H(6)CuN(3)S(2), monoclinic, P2(1)/c, a = 7.864(3) A, b = 14.328(6) A, c = 6.737(2) A, beta = 100.07(3) degrees , V = 747.4(5), Z = 4, R = 0.0363; 3, C12H24Br2Cu2N8S4, monoclinic, C2/c, a = 19.420(7) A, b = 7.686(3) A, c = 16.706(6) A, beta = 115.844(6) degrees , V = 2244.1(14) A(3), Z = 4, R = 0.0228; 4, C12H24Cl2Cu2N8S4, monoclinic, P2(1)/c, a = 7.4500(6) A, b = 18.4965(15) A, c = 16.2131(14) A, beta = 95.036(2) degrees , V = 2225.5(3) A(3), Z = 4, R = 0.0392. The 3D polymer 2 exhibits 20-membered metallacyclic rings in its structure, while synthesis of linear polymers, 1 and 1a, represents an unusual example of I (1a)-S (1) bond isomerism.     

Synthesis and X-ray Powder Structures of Two Lamellar Copper Arylenebis(phosphonates)

Reaction of copper salts with 1,4-phenylenebis(phosphonic acid) yielded a conventional layered compound, Cu(2)[(O(3)PC(6)H(4)PO(3))(H(2)O)(2)], while a similar reaction with 4,4'-biphenylenebis(phosphonic acid) resulted in a new lamellar structure with composition Cu[HO(3)P(C(6)H(4))(2)PO(3)H]. The structures of these compounds were solved ab initio by using X-ray powder diffraction data. The crystals of the phenylenebis(phosphonate) compound are monoclinic, space group C2/c, with a = 18.8892(4) ?, b = 7.6222(2) ?, c = 7.4641(2) ?, beta = 90.402(2) degrees, and Z = 4. The layer structure in this case is similar to that in copper phenylphosphonate, Cu[O(3)PC(6)H(5)]. The metal atoms display a distorted square pyramidal geometry where four of the coordination sites are occupied by the phosphonate oxygens. The remaining site is filled by an oxygen atom of the water molecule. Adjacent metal-O(3)PC layers are covalently pillared by the phenyl group of the phosphonates to create a 3-dimensional structure. Cu[HO(3)P(C(6)H(4))(2)PO(3)H] is triclinic, space group P&onemacr;, with a = 4.856(2) ?, b = 14.225(5) ?, c = 4.788(2) ?, alpha = 97.85(1) degrees, beta = 110.14(1) degrees, gamma = 89.38(1) degrees, and Z = 1. The structure in this case, ideally consists of linear chains of copper atoms. The copper atoms are bridged by centrosymmetrically related phosphonate groups utilizing two of their oxygen atoms. This binding mode leads to square planar geometry for the copper atoms. The third oxygen atom of the phosphonate is protonated and is involved in linking adjacent linear chains through hydrogen bonds. At the same time, these hydroxyl oxygens interact weakly (Cu-O = 3.14 ?) with the copper atoms of the adjacent chain. Considering these long Cu-O interactions, the geometry of the copper atom may be described as distorted square bipyramidal. As in the phenylphosphonate structure, the biphenyl groups covalently link the Cu-O(3)PC networks in the perpendicular direction.     

Synthesis and Crystal Structure of a Dinuclear Cu(Ⅱ) Complex [Cu(C_(13)H_9N_2O)Cl]_2·(CH_3CN)_2 with Ligand 2-Benzimidazol

A new dinuclear copper complex, [Cu(C13H9N2O)Cl]2·(CH3CN)2 (C30H24Cl2Cu2N6O2), has been synthesized and characterized by X-ray structure determination. It crystallizes in the tricli- nic system, space group P1, with a = 7.6677(14), b = 9.2375(17), c = 11.227(2) , α = 81.338(3), β = 88.173(4), γ = 66.199(3)o, V = 718.9(2) 3, Z = 1, Mr = 698.53, F(000) = 354, Dc = 1.613 g/cm3, μ(MoKα) = 1.705 mm-1, the final R = 0.0645 and wR = 0.1364 for 2474 unique reflections with 1809 observed ones (I > 2σ(I)). In the title complex, each copper(II) atom is located at the center of a distorted tetrahedron consisting of four coordinate atoms (one nitrogen atom, two oxygen anions, and one chlorine atom). Two copper(II) atoms are bridged by two oxygen anions (O(1) and O(1a)) of two phenolates to form a Cu(II)–Cu(II) binuclear entity, and the distance between two copper(II) atoms is 3.0144(15) .     

Monomeric Bis(eta(2)-alkyne)copper(I) and -silver(I) Halides, Pseudohalides, and Arenethiolates

The synthesis and characterization of the complexes [(eta(5)-C(5)H(4)SiMe(3))(2)Ti(C&tbd1;CSiMe(3))(2)]MX (M = Cu, X = OTf (2), SC(6)H(5) (4), SC(6)H(4)NMe(2)-2 (5), SC(6)H(4)CH(2)NMe(2)-2 (6), S-1-C(10)H(6)NMe(2)-8 (7), Cl (8), (N&tbd1;CMe)PF(6) (9); M = Ag, X = OTf (3)) are described. These complexes contain monomeric MX entities, which are eta(2)-bonded by both alkyne functionalities of the organometallic bis(alkyne) ligand [(eta(5)-C(5)H(4)SiMe(3))(2)Ti(C&tbd1;CSiMe(3))(2)] (1). The reactions of 2 with the Lewis bases N&tbd1;CPh and N&tbd1;CC(H)=C(H)C&tbd1;N afford the cationic complexes {[(eta(5)-C(5)H(4)SiMe(3))(2)Ti(C&tbd1;CSiMe(3))(2)]Cu(N&tbd1;CPh)}OTf (10) and {[(eta(5)-C(5)H(4)SiMe(3))(2)Ti(C&tbd1;CSiMe(3))(2)]Cu}(2)(N&tbd1;CC(H)=C(H)C&tbd1;N)(OTf)(2) (11), respectively. The X-ray structures of 2, 3, and 6 have been determined. Crystals of 2 are monoclinic, space group P2(1)/c, with a = 12.8547(7) ?, b = 21.340(2) ?, c = 18.279(1) ?, beta = 133.623(5) degrees, V= 3629.7(5) ?(3), Z = 4, and final R = 0.047 for 5531 reflections with I >/= 2.5sigma(I) and 400 variables. The silver triflate complex 3 is isostructural, but not isomorphous, with the corresponding copper complex 2, and crystals of 3 are monoclinic, space group P2(1)/c, with a = 13.384(3) ?, b = 24.55(1) ?, c = 13.506(3) ?, beta = 119.21(2) degrees, V = 3873(2) ?(3), Z = 4, and final R = 0.038 for 3578 reflections with F >/= 4sigma(F) and 403 variables. Crystals of the copper arenethiolate complex 6 are triclinic, space group P&onemacr;, with a = 11.277(3) ?, b = 12.991(6) ?, c = 15.390(6) ?, alpha = 65.17(4) degrees, beta = 78.91(3) degrees, gamma = 84.78(3) degrees, V = 2008(2) ?(3), Z = 2, and final R = 0.079 for 6022 reflections and 388 variables. Complexes 2-11 all contain a monomeric bis(eta(2)-alkyne)M(eta(1)-X) unit (M = Cu, Ag) in which the group 11 metal atom is trigonally coordinated by the chelating bis(eta(2)-alkyne) entity Ti(C&tbd1;CSiMe(3))(2) and an eta(1)-bonded monoanionic ligand X. The copper arenethiolate complexes 4-7 are fluxional in solution.     

Synthesis and Crystal Structure of Tri(4-(3-hydroxy2-ethyl-4-pyridinone-1-yl)-aniline Condensation Salicylaldehydato) Monohydratotricopper(II)Dimethylformamide Monohydrate Solvate

1 INTRODUCTION Synthesis of transition-metal complexes with Schiff-base has been a subject of considerable im- portance[1, 2]. These complexes are not only good coordination agents for Schiff-base, but also good bactericide and antitumour agent[3, 4]. A number of hydroxypyridinones are nontoxic compounds that have been applied in bioinorganic chemistry over many years[5], and their iron(III) complexes have been assessed for the amelioration of anaemia[6]. They have also been examined …     

Synthesis, Structure and DFT Investigation into a Copper(II) Compound Consisting of 4,7-diphenyl-1,10-phentheanthroline

1 INTRODUCTION terested in the unique effects associated with substituents at 4- and 7-positions of the phenan- The coordination chemistry of 1,l0-phenanthroline throline ring. Thus, when phenyl groups are present, and its derivatives has captured the attention of che- the absorptivities of the CT transitions are increased mists for years. The reports on biological importance[1~4], markedly due to the extension of the dipole moment supramolecular chemistry[5], electronic spectra[6], conne…     

Synthesis and Crystal Structure of Dinuclear Copper Complex[Cu（CH2O（C6H4）N=C（C6H4）O）（Py]2

1 INTRODUCTION Synthesis of transition metal complexes with Schiff-base has been a subject of considerable importance [1,2]. They are not only good complexing agents for Schiff-base, but also good bactericide and antitumour agent [3,4]. At present, there is a spectacular growth in this field. Recently, some bridged binuclear complexes have received much attention on account of their biological relevance and condensed-phase magnetic properties[5,6]. Especially, the complexes containin…     

Synthesis and Crystal Structure of Bis（μ-bis（diphenylphosphino）methane）（μ-benzenethiolate）（acetonitrile） Dicopper（I） Perchlorate Diethylether Solvate

1INTRODUCTIONTherehasbeenincreasinginterestindesigningpolymetalliccomplexeswithmixeddiphosphineandthiolateligandsowingtotheuniqueopticalandoptoelectronicproperties[1].Itiswell-knownthatthiolatesasversatilebridgingligandscanexhibitvariousbondingmodestoprod…     

Synthesis and Structural Characterization of a Salt {[Co(Phen)_3][Mo_2S_2(μ-S)_2(edt)_2]}_2·(DMSO)_2·(Et_2O)(Phen = 1,10-Phenanthroline,edt=Ethane-1,2-dithiolate)

1 INTRODUCTION Dinuclear sulfido-bridged complexes with M2S2(μ-S)2 unit serving as building blocks for the construction of mixed-metal clusters are well docu- mented due to their rich structure diversities[1～3] as well as their potential applications in catalytic sys- tems and eletro/photonic materials[4, 5]. For example, reaction of [CpEt2Mo2S2(μ-S)2] with 2 equiv. of Co- (CO)3(NO) gave rise to a cubane-like cluster com- pound [CpEt2Mo2S2(μ-S)2Co2(CO)2][6]. In the case of[Mo…     

Copper and Bismuth Complexes Containing Dipyridyl gem-Diolato Ligands: Bi(III)(2)[(2-Py)(2)CO(OH)](2)(O(2)CCF(3))(4)(THF)(2), Cu(II)[(2-Py)(2)CO(OH)](2)(HO(2)CCH(3))(2), and Cu(II)(4)[(2-Py)(2)CO(OH)](2)(O(2)CCH(3))(6)(H(2)O)(2), a Ferromagnetically Coupled Tetranuclear Copper(II) Chain

The reactions of the singly deprotonated di-2-pyridylmethanediol ligand (dpmdH(-)) with copper(II) and bismuth(III) have been investigated. A new dinuclear bismuth(III) complex Bi(2)(dpmdH)(2)(O(2)CCF(3))(4)(THF)(2), 1, has been obtained by the reaction of BiPh(3) with di-2-pyridyl ketone in the presence of HO(2)CCF(3) in tetrahydrofuran (THF). The reaction of Cu(OCH(3))(2) with di-2-pyridyl ketone, H(2)O, and acetic acid in a 1:2:2:2 ratio yielded a mononuclear complex Cu[(2-Py)(2)CO(OH)](2)(HO(2)CCH(3))(2), 2, while the reaction of Cu(OAC)(2)(H(2)O) with di-2-pyridyl ketone and acetic acid in a 2:1:1 ratio yielded a tetranuclear complex Cu(4)[(2-Py)(2)CO(OH)](2)(O(2)CCH(3))(6)(H(2)O)(2), 3. The structures of these complexes were determined by single-crystal X-ray diffraction analyses. Three different bonding modes of the dpmdH(-) ligand were observed in compounds 1-3. In 2, the dpmdH(-) ligand functions as a tridentate chelate to the copper center and forms a hydrogen bond between the OH group and the noncoordinating HO(2)CCH(3) molecule. In 1 and 3, the dpmdH(-) ligand functions as a bridging ligand to two metal centers through the oxygen atom. The two pyridyl groups of the dpmdH(-) ligand are bound to one bismuth(III) center in 1, while in 3 they are bound two copper(II) centers, respectively. Compound 3 has an unusual one dimensional hydrogen bonded extended structure. The intramolecular magnetic interaction in 3 has been found to be dominated by ferromagnetism. Crystal data: 1, C(38)H(34)N(4)O(14)F(12)Bi(2), triclinic P&onemacr;, a = 11.764(3) ?, b = 11.949(3) ?, c = 9.737(1) ?, alpha =101.36(2) degrees, beta = 105.64(2) degrees, gamma = 63.79(2) degrees, Z = 1; 2, C(26)H(26)N(4)O(8)Cu/CH(2)Cl(2), monoclinic C2/c, a = 25.51(3) ?, b = 7.861(7) ?, c = 16.24(2) ?, beta = 113.08(9) degrees, Z = 4; 3, C(34)H(40)N(4)O(18)Cu(4)/CH(2)Cl(2), triclinic P&onemacr;, a = 10.494(2) ?, b = 13.885(2) ?, c = 7.900(4) ?, alpha =106.52(2) degrees, beta = 90.85(3) degrees, gamma = 94.12(1) degrees, Z = 1.     

Versatility of heterocyclic thioamides in the construction of a trinuclear cluster [Cu3I3(dppe)3 (SC5H4NH)] and Cu(I) linear polymers {Cu6(SC5H4NH)6I6}n x 2nCH3CN and {Cu(I)6 (SC3H6N2)6X6}n (X = Br, I)

Reaction of copper(I) iodide with pyridine-2-thione (2-SC5H4NH) and 1,2-bis(diphenylphosphino)ethane (dppe) in a CH3CN-CHCl3 mixture yielded a triangular cluster, [Cu3I3(mu2-P,P-dppe)3 (eta1-SC5H4NH)], 1. Similar reaction with 2-SC5H4NH and a series of diphosphanes, Ph2P-X-Ph2P {X = -CH2- (dppm), -(CH2)3- (dppp), -(CH2)4- (dppb), -CH=CH- (dppen)}, gave a novel iodo-bridged hexanuclear Cu(I) linear polymer,{Cu6(mu3-SC5H4NH)4 (mu2-SC5H4NH)2 (I4)(mu-I)2-}n x 2nCH3CN, 2. Reactions of copper(I) iodide/copper(I) bromide with 1,3-imidazolidine-2-thione (SC3H6N2) in a CH3CN-CHCl3 mixture yielded hexanuclear Cu(I) linear chain polymers, [{Cu6(mu3-SC3H6N2)2 (mu2-SC3H6N2)4X2 (mu-X)4}n] (X = Br, 4; I, 5). In compound 1, two iodide atoms and one dppe form the dinuclear Cu(mu2-I)2 (mu2-dppe)Cu core, and two dppe ligands bridge this core with the third Cu(I) center coordinated to 2-SC5H4NH via the S atom. The chain polymer 2 has a centrosymmetric hexanuclear central core, Cu6S6I4 (mu-I)2--, formed by dimerization of six-membered trinuclear motifs, Cu3(mu2-SC3H6N2)3I3 via (mu3-S) bonding modes of the thione ligand, and has four terminal and two bridging iodine atoms in trans-orientations. Linear chains are separated by the nonbonded acetonitrile molecules. In 4 and 5, three copper(I) bromide or copper(I) iodide moieties and three SC3H6N2 ligands combined via bridging S donor atoms to form the six-membered trinuclear Cu3(mu2-SC3H6N2)3I3 cores which polymerized via S and X atoms in a side-on fashion to form linear chain polymers, [{Cu6(mu3-SC3H6N2)2 (mu2-SC3H6N2)4X2(mu-X)4}n]. The (mu3-S) modes of bonding of neutral heterocyclic thioamides are first examples, as are trinuclear cluster and linear polymers rare examples in copper chemistry.     

Synthesis, Characterization, and Crystal Structures of New Dications Bearing the -Se-Se- Bridge

Starting from 1,3-dimethyl-4-imidazoline-2-selone (1), 1,2-bis(2-selenoxo-3-methyl-4-imidazolinyl-2-)ethane (3) and 1,3-dimethylimidazolidine-2-selone (4), the following six compounds, [(C(5)H(8)N(2)Se-)(2)](2+).2Br(-) (I), [(C(5)H(8)N(2)Se-)(2)](2+).2I(-) (II), [(C(5)H(8)N(2)Se-)(2)](2+).Cl(-).I(3)(-) (III) [(C(5)H(10)N(2)Se-)(2)](2+).Br(-).IBr(2)(-) (IV), [(C(5)H(7)N(2)Se-)(2)](2+).I(3)(-).(1)/(2)I(4)(-) (V) and [(C(5)H(7)N(2)Se-)(2)](2+).2I(-).CH(3)CN (VI), in which the selenium compounds are oxidized to dications bearing the uncommon -Se-Se- bridge, have been prepared, and I-V crystallographically characterized. I and III were obtained by reacting 1 with IBr and ICl respectively, while II was obtained by reduction of previously described hypervalent selenium compound of 1 (5) bearing the I-Se-I group with elemental tellurium. These three compounds contain the same [(C(5)H(8)N(2)Se-)(2)](2+) dication balanced by two bromides in I, two iodides in II, and Cl(-) and I(3)(-) in III. However, on the basis of the Se-Cl bond length of 2.778(5) ?, III can also be considered as formed by the [(C(5)H(8)N(2)Se-)(2)Cl](+) cation, with I(3)(-) as counterion. Similarly to III, compound IV, which was obtained by reacting 4 with IBr, can be considered as formed by [(C(5)H(10)N(2)Se-)(2)Br](+) cations and IBr(2)(-) anions. As in II, compound V has been prepared by reduction of the hypervalent selenium compound of 3 (6) bearing two I-Se-I groups with elemental tellurium. In V, the [(C(5)H(7)N(2)Se-)(2)](2+) cation is balanced by I(3)(-) and half I(4)(2-) anions. The structural data show that all the cations are very similar, with Se-Se bond lengths ranging from 2.409(2) to 2.440(2) ?. FT-IR and FT-Raman spectra of I-VI allow one to identify two bands around 230 +/- 10 and 193 +/- 5 cm(-1) that are common to all compounds. These bands are generally strong in the FT-Raman and weak in the FT-IR spectra and should contain a contribution of the nu(Se-Se) stretching vibration. The spectra are also in good agreement with the structural features of the polyhalide anions present in the crystals. Crystallographic data are as follows: I is monoclinic, space group P2(1), with a = 9.849(6) ?, b = 11.298(5) ?, c = 7.862(6) ?, beta = 106.44(2) degrees, Z = 2, and R = 0.0362; II is monoclinic, space group P2(1), with a = 8.063(6) ?, b = 11.535(5) ?, c = 10.280(5) ?, beta = 107.13(2) degrees, Z = 2, and R = 0.0429, III is monoclinic, space group P2(1)/n, with a = 10.431(7) ?, b = 18.073(5) ?, c = 11.223(6) ?, beta = 100.76(2) degrees, Z = 4, and R = 0.0490; IV is monoclinic, space group P2(1)/n, with a = 10.298(5) ?, b = 18.428(7) ?, c = 11.475(6) ?, beta = 104.10(4) degrees, Z = 4, and R = 0.0300; V is triclinic, space group P&onemacr;, with a = 7.456(6) ?, b = 11.988(5) ?, c = 12.508(5) ?, alpha = 79.32(2) degrees, beta = 85.49(2) degrees, gamma = 80.62(2) degrees, Z = 2, and R = 0.0340.     

A New Dinuclear Cu(Ⅱ) Complex of a Ligand with Benzimidazole Group─Synthesis and Crystal Structure

A new dinuclear copper complex, [Cu(C9H11N3)Cl2]2 (C18H22Cl4Cu2N6), has been synthe- sized and characterized by X-ray structure determination. It crystallizes in the triclinic P1 space group with a = 7.526(3), b = 9.473(4), c = 9.535(3) , α = 117.214(10), β = 108.251(9), γ = 91.560(6)o, V = 562.3(4) 3, Z = 1, Mr = 591.30, F(000) = 298, Dc = 1.746 g/cm3, μ(MoKα) = 2.385 mm-1, the final R = 0.0577 and wR = 0.1248 for 2188 unique reflections with 1629 observed ones (I > 2σ(I)). In the title complex, each copper(II) atom is located at the center of a distorted trigonal bipyramid of five coordination atoms (two nitrogen and three chlorine atoms). Two copper(II) atoms were bridged by two chlorine anions (Cl(2) and Cl(2a)) to form a Cu(II)-Cu(II) binuclear entity with the distance between two copper(II) atoms of 3.398 .     

Synthesis and Crystal Structure of Bis(μ-bis(diphenyl-phosphino)methane)(μ-benzenethiolate)(acetonitrile)Dicopper(I) Perchlorate Diethylether Solvate

The reaction between [Cu2(μ-dppm)2(MeCN)4](ClO4)2(dppm=bis(diphenylphos-phino)methane) and [Zn(PhS)2(bpy)] (bpy=2,2'-bipyridine,PhS=benzenethiolate) gave the complex [Cu2(μ-dppm)2(μ-PhS)(MeCN)]ClO4·0.5(Et2O)(C58H52ClNO4P4SCu2·0.5Et2O) which was determined by X-ray single-crystal diffraction.The crystal is of orthorhombic,space group P212121 with a=13.6157(3),b=20.8022(6),c=21.3299(6)A,V=6041.4(3) A3,Mr=1182.54,Dc=1.300 g/cm3,F(000)=2444,μ=0.934 mm-1 and Z=4.The final R=0.0773 and wR=0.1843 for 7744 observed reflections (I>2σ(I)).The dicopper atoms are doubly bridged by dppm as well as one S donor from benzenethiolate.One copper atom is in a distorted trigonal bipyramidal environ- ment,whereas the other adopts a distorted tetrahedral geometry.     

Imide Transfer Properties and Reactions of the Magnesium Imide ((THF)MgNPh)(6): A Versatile Synthetic Reagent

Imide transfer properties of ((THF)MgNPh)(6) (1) and the synthesis of the related species {(THF)MgN(1-naphthyl)}(6).2.25THF (2), via the reaction of dibutylmagnesium with H(2)N(1-naphthyl), in a THF/heptane mixture are described. Treatment of 1 with Ph(2)CO, 4-Me(2)NC(6)H(4)NO, t-BuNBr(2) (3), PCl(3), or MesPCl(2) (Mes = 2,4,6-Me(3)C(6)H(2)-) leads to the isolation of Ph(2)CNPh (4), 4-Me(2)NC(6)H(4)NNPh (5), t-BuNNPh (6), (PhNPCl)(2) (7), or (MesPNPh)(2) (8) in moderate yield. Reaction between 1 and GeCl(2).dioxane, SnCl(2), or PbCl(2) affords the M(4)N(4) (M = Ge, Sn, Pb) cubane imide derivative (GeNPh)(4) (9), [(SnNPh)(4).{MgCl(2)(THF)(4)}](infinity) (10), (SnNPh)(4).0.5PhMe (11), or (PbNPh)(4).0.5PhMe (12). Interaction of 1 with Ph(3)PO, (Me(2)N)(3)PO, or Ph(2)SO furnishes the complex (Ph(3)POMgNPh)(6) (13), {(Me(2)N)(3)POMgNPh}(6).2PhMe (14), or (Ph(2)SOMgNPh)(6) (15). The addition of 3 equiv of MgBr(2) to 1 gives 1.5 equiv of ((THF)Mg)(6)(NPh)(4)Br(4) (16) in quantitative yield, whereas treatment of 16 with 4 equiv of 1,4-dioxane is an alternative synthetic route to 1. Compounds 2, 3, 9, 10, and 14 were characterized by X-ray crystallography. The reactions demonstrate that 1 is a versatile and useful reagent for the synthesis of a variety of main group imides. Crystal data at 130 K with Mo Kalpha (lambda = 0.710 73 ?) radiation for 3 or Cu Kalpha (lambda = 1.541 78 ?) radiation for 2, 9, 10, and 14: 2, C(93)H(108)Mg(6)N(6)O(7.25), a = 28.101(7) ?, b = 35.851(7) ?, c = 36.816(7) ?, Z = 2, space group Fddd, R = 0.068 for 3500 (I > 2sigma(I)) data; 3, C(4)H(9)Br(2)N, a = 6.682(2) ?, b = 10.834(3) ?, c = 11.080(3) ?, alpha = 66.25(2) degrees, beta = 89.88(2) degrees, gamma = 82.53(2) degrees, Z = 4, space group P&onemacr;, R = 0.038 for 2043 (I > 2sigma(I)) data; 9, C(24)H(20)Ge(4)N(4), a = 10.749(2) ?, b = 12.358(3) ?, c = 35.818(7) ?, Z = 8, space group Pbca, R = 0.040 for 2981 (I > 2sigma(I)) data; 10, C(40)H(52)Cl(2)MgN(4)O(4)Sn(4), a = 12.770(3) ?, b = 13.554(3) ?, c = 25.839(5) ?, Z = 4, space group P2(1)2(1)2(1), R = 0.040 for (I > 2sigma(I)) data; 14, C(86)H(154)Mg(6)N(4)O(6)P(6), a = 22.478(4) ?, b = 16.339(3) ?, c = 29.387(6) ?, Z = 4, space group Pbcn, R = 0.081 for 4696 (I >2sigma(I)) data.