Tetranuclear silver(I) clusters showing high ionic conductivity in a bicontinuous cubic mesophase.

The synthesis and characterization of tetranuclear silver triazole metallomesogens, [Ag4(L(4)-C(n))6][BF4]4 (L(4)-C(n) = 4-alkyl-1,2,4-triazoles where C(n) stands for C(n)H(2n+1) with n = 12, 14, 16, and 18), are reported. Upon heating, a phase transition sequence of Cr → SmC → Cub → SmA → isotropic liquid is observed for all of these compounds. Depending on the alkyl chain length, two types of cubic phases are found in this series of compounds.

Oxygenation of ruthenium carbene complexes containing naphthothiophene or naphthofuran: spectroscopic and DFT studies.

The aryl propargylic alcohol 1-[2-(thiophen-3-yl)phenyl]prop-2-yn-1-ol (1a) is readily prepared from 2-(thiophen-3-yl)benzaldehyde. In the presence of visible light, treatment of 1a with one-half mole equivalent of [Ru]Cl ([Ru]=Cp(dppe)Ru) (dppe=1,2-bis(diphenylphosphino)ethane) and NH4PF6 in O2 affords the naphtha[2,1-b]thiophene-4-carbaldehyde (4a) in high yields. The cyclization reaction of 1a proceeds through the formation of the carbene complex 2a that contains the naphtha[2,1-b]thiophene ring, which is isolated in a 1:1 stoichiometric reaction.

Tetra-kis[μ-1,3-bis-(4,5-dihydro-1,3-oxazol-2-yl)benzene-κ(2)N:N']tris-ilver(I) tris-(hexa-fluoridophosphate).

In the title compound, [Ag(3)(C(12)H(12)N(2)O(2))(4)](PF(6))(3), one Ag(I) ion, lying on a twofold rotation axis, is coordinated by four N atoms from four 1,3-bis-(4,5-dihydro-1,3-oxazol-2-yl)benzene (L) ligands in a distorted tetra-hedral geometry and the other Ag(I) ion is coordinated by two N atoms from two L ligands in a bent arrangement [N-Ag-N = 169.03 (17)°]. Two L ligands adopt a syn conformation, while the other two adopt an anti conformation.

catena-Poly[[bis-(nitrato-κO)copper(II)]-μ-1,4-bis-(4,5-dihydro-1,3-oxazol-2-yl)-benzene-κN:N'].

In the title coordination polymer, [Cu(NO(3))(2)(C(12)H(12)N(2)O(2))](n), the Cu(II) ion, situated on an inversion center, is coordinated by two O atoms from two nitrate anions and two N atoms from two 1,4-bis-(4,5-dihydro-1,3-oxazol-2-yl)benzene (L) ligands in a distorted square-planar geometry. Each L ligand also lies across an inversion center and bridges two Cu(II) ions, forming a polymeric chain running along the [101] direction. The three O atoms of the nitrate group are disordered over two positions in a 3:2 ratio.

An eleven-vertex deltahedron with hexacapped trigonal bipyramidal geometry.

The first elemental cluster with hexacapped trigonal bipyramidal geometry is revealed in the luminescent undecanuclear silver complex which is stabilized by nine dithiocarbamate ligands and has an interstitial hydride. The hydride position within the Ag(11) cage is confirmed by a DFT investigation.

Anion-templated syntheses of octanuclear silver clusters from a silver dithiophosphate chain.

Extended chain polymers [Ag(5){S(2)P(OEt)(2)}(4)(PF(6))](n), (1) could be converted to clusters of the type, [Ag(8)(X){S(2)P(OEt)(2)}(6)](PF(6)) [X = F (2); Cl (3); H (4)], by the addition of appropriate anions, of which [Ag(8)(H){S(2)P(OEt)(2)}(6)](+) showed a unique tetracapped-tetrahedral Ag(8) core and contained Ag-mu-H-Ag linkages.

Structure, photophysical properties, and DFT calculations of selenide-centered pentacapped trigonal prismatic silver(I) clusters.

Undecanuclear silver clusters [Ag(11)(mu(9)-Se)(mu(3)-Br)(3){Se(2)P(OR)(2)}(6)] (R = Et, (i)Pr, (2)Bu) were isolated from the reaction of [Ag(CH(3)CN)(4)](PF(6)), NH(4)[Se(2)P(OR)(2)], and Bu(4)NBr in a molar ratio of 4:3:1 in CH(2)Cl(2) at -20 degrees C. Clusters were characterized by elemental analysis, NMR spectroscopy ((1)H, (31)P, and (77)Se), positive FAB mass spectrometry, and X-ray crystallography of the isopropyl derivative. Structural elucidations revealed that the Ag(11)Se core geometry of clusters is a selenide-centered, slightly distorted 3,3,4,4,4-pentacapped trigonal prism surrounded by six diselenophosphato ligands, each in a tetrametallic tetraconnective (mu(2), mu(2)) coordination mode, and three mu(3)-bromide anions.

Tetra-butyl-ammonium bis-[4,4'-dimethyl-2,2'-(3,7-dimethyl-1H-4,2,1-benzothiaza-siline-1,1-di-yl)dibenzene-thiol-ato]vanadium(III) acetonitrile tetra-solvate.

In the title compound, [N(C(4)H(9))(4)][V(C(23)H(21)NS(3)Si)(2)]·4CH(3)CN, the V(III) atom (site symmetry ) is coordinated by two N,S,S'-tridentate 4,4'-dimethyl-2,2'-(3,7-dimethyl-1H-4,2,1-benzothiaza-siline-1,1-di-yl)dibenzene-thiol-ate ligands in a distorted trans-VN(2)S(4) octa-hedral geometry. The complete cation is generated by crystallographic twofold symmetry, with the V atom lying on the rotation axis. The unusual ligand arose from nucleophilic attack on the coordinated nitrile by the thiol-ate precursor and reduction of nitrile to the imidate.

Octanuclear copper(I) clusters inscribed in a Se(12) icosahedron: anion-induced modulation of the core size and symmetry.

Synthesis and structural characterization of an octanuclear Cu(I) cluster [Cu(8){Se(2)P(O(i)Pr)(2)}(6)](PF(6))(2) (1) with an empty Cu(8) cubic core involving diisopropyl diselenophosphate (dsep) ligand has been demonstrated despite its high tendency to abstract anions even from the traces of impurities in the solvent. Reaction of 1 with anion sources (Bu(4)NF for F(-); NaBH(4) for H(-), and NaSH for S(2-)) in a 1:1 ratio produced anion-centered Cu(8) clusters with a formula [Cu(8)(X){Se(2)P(O(i)Pr)(2)}(6)](PF(6)) (X = F, 2a; H, 3a; D, 3a') and [Cu(8)(S){Se(2)P(O(i)Pr)(2)}(6)] (4) in high yields. In addition, fluoride- and hydride-centered Cu(8)(I) clusters [Cu(8)(X){Se(2)P(OEt)(2)}(6)](PF(6)) (X = F, 2b; H, 3b) could be generated in approximately 80% yield by direct reaction of [Cu(CH(3)CN)(4)](PF(6)), NH(4)Se(2)P(OEt)(2), and the anion sources (Bu(4)NF for F(-); NaBH(4) for H(-)) in 8:6:1 ratio.

Conjugate base of a secondary phosphine selenide [P(Se)(O(i)Pr)2]- as the bridging unit for the construction of heterometallic Fe(II)-Hg(II)/Cd(II) complexes.

Reactions of perchlorate salts of Hg(II)/Cd(II) with [CpFe(CO)(2)P(Se)(O(i)Pr)(2)] (denoted as L) produced dicationic clusters [HgL(2)](ClO(4))(2), 1; [HgL(3)](ClO(4))(2), 2; and [CdL(3)(H(2)O)](ClO(4))(2), 11. However, the reactions of L with Hg(II)/Cd(II) halides yielded neutral complexes. For instance, HgI(2) produced [Hg(3)I(6)L(2)], 3, or [HgI(2)L(2)], 4, depending on the metal-to-ligand ratio used.

Facile entrapment of a hydride inside the tetracapped tetrahedral Cu(I)8 cage inscribed in a S12 icosahedral framework.

Reaction of [Cu(CH(3)CN)(4)](PF(6)) and NH(4)[S(2)P(OR)(2)] in a 4:3 ratio in acetone at room temperature produces octanuclear dicationic copper complexes [Cu(8){S(2)P(OR)(2)}(6)](PF(6))(2) (R = (i)Pr, 1; Et, 3) in 81 and 83% yields, respectively. On the other hand, reaction of [Cu(CH(3)CN)(4)](PF(6)), NH(4)[S(2)P(OR)(2)], and NaBH(4) in an 8:6:1 molar ratio in THF for 1 h yields [Cu(4)(H)(mu(3)-Cu)(4){S(2)P(OR)(2)}(6)](PF(6)) (R = (i)Pr, 2a; Et, 4a) in 87 and 82% yields, respectively. In a similar reaction when NaBD(4) is used instead of NaBH(4), [Cu(4)(D)(mu(3)-Cu)(4){S(2)P(OR)(2)}(6)](PF(6)) (R = (i)Pr, 2b; Et, 4b) are obtained in 83 and 78% yields, respectively.

A novel cyclometalated dimeric iridium complex, [(dfpbo)2Ir]2 [dfpbo = 2-(3,5-difluorophenyl)benzoxazolato-N,C2'], containing an unsupported Ir(II)-Ir(II) bond.

An unusual iridium complex, [(dfpbo)(2)Ir](2) [dfpbo = 2-(3,5-difluorophenyl)benzoxazolato-N,C(2')], which is the first dimeric iridium complex composed of two bis-cyclometalated Ir(II) structures connected by an unsupported Ir(II)-Ir(II) bond, has been synthesized and fully characterized. Under mild conditions of neutral pH at room temperature, this complex dissociated spontaneously to form the stable radical [Ir(dfpbo)(2)]*.

N,N-Bis(6-methyl-2-pyrid-yl)formamidine.

In the crystal structure of the title mol-ecule, C(13)H(14)N(4), the two pyridyl rings are not coplanar but twisted about the C-N bond with an inter-planar angle of 71.1 (1)°. In the crystal, the mol-ecules form dimers, situated on crystallographic centres of inversion, which are connected via a pair of N-H⋯N hydrogen bonds.

2-{5-[N-(2-Pyridyl)carbamo-yl]pentan-amido}pyridinium hexa-fluoro-phosphate.

In the crystal structure of the title compound, C(16)H(19)N(4)O(2) (+)·PF(6) (-), the cations and anions are situated on centres of inversion. Thus, the N-H H atom is disordered over both N atoms due to symmetry. In the crystal, mol-ecules are connected via N-H⋯F and N-H⋯O hydrogen bonds.

N,N-Bis(2-pyrid-yl)formamidine.

In the crystal structure of the title compound, C(11)H(10)N(4), the dihedral angle between the two pyridyl rings is 36.1 (1)°. The mol-ecules are connected via two strong N-H⋯N and two weak C-H⋯N hydrogen bonds into dimers, which are located on centers of inversion.

Syntheses, structures and magnetism of linear tri- and tetra-copper chains containing anions of N,N'-bis(pyrimidine-2-yl)formamidine.

Reaction of Kpmf (pmf(-) = anion of N,N'-bis(pyrimidyl-2-yl)formamidine, Hpmf) with divalent copper salt CuX2 afforded the linear trinuclear complexes of the type [Cu3(pmf)4](X)2 (X = BF4, 1; NO3, 2; ClO4, 3), while reaction of Kpmf with monovalent copper salt CuX gave the linear tetranuclear complexes of the type Cu4(pmf)4X2 (X = Cl, 4; Br, 5). The copper atoms of complexes 1-5 are helically bridged by four pmf(-) ligands, resulting in three different coordination modes for the pmf(-) ligands. In complexes 1-3, one pmf(-) ligand adopts a new coordination mode with the two amine nitrogen atoms chelating to the central copper atom, while the other three feature chelation by one pyrimidyl and one adjacent amine nitrogen atoms.

Toward quartz and cristobalite: spontaneous resolution, structures, and characterization of chiral silica-mimetic silver(I)-organic materials.

An alpha-quartz-mimetic chiral coordination network of [Ag(L1)(CF3SO3)]n (L1=5,5'-bipyrimidine), after treatment with PF6- anions, undergoes a solution-state structural transformation toward [Ag(L1)(PF6)]n with a cristobalite-mimetic chiral structures. This structural transformation is accompanied by substantial enhancement in the fluorescent intensity and in the second-harmonic-generation response. The results also demonstrate an effective design strategy based on the spontaneous resolution route for the preparation of chiral architectures.

Crystal structures and solution behaviors of dinuclear d(10)-metal complexes containing anions of N,N'-bis(pyrimidine-2-yl)formamidine.

The salts of Zn(II), Cd(ii) and Hg(II) react instantaneously with Kpmf (pmf(-) = anion of N,N'-bis(pyrimidine-2-yl)formamidine, Hpmf) in THF, producing bimetallic complexes of the types [M(2)(pmf)(3)](X) (M = Zn(II), X = I(3)(-), ; M = Zn(II), X = NO(3)(-), ; M = Zn(II), X = ClO(4)(-), ; M = Cd(II), X = NO(3)(-), ; M = Cd(II), X = ClO(4)(-), ) and Hg(2)(pmf)(2)X(2) (X = Cl, ; Br, ; I, ). New tridentate and tetradentate coordination modes were observed for the pmf(-) ligands and their fluxional behaviors investigated by measuring variable-temperature (1)H NMR spectra. Complexes and , which possess only tetradentate coordination modes for the pmf(-) ligands in the solid state show larger free energy of activation (DeltaG(c)( not equal)) for the exchange than complexes and with tetradentate and/or tridentate coordination modes.

Novel metalloreagent Cp(CO)2FeP(Se)(OR)2 produced from P-Se bond cleavage in the thermal reaction of [CpFe(CO)2]2 with phosphor-1,1-diselenolates.

The reaction of [CpFe(CO)2]2 with NH4Se2P(OR)2 yields a novel reagent Cp(CO)2FeP(Se)(OR)2, which has demonstrated coordination properties at the Se center to form heterometallic clusters as well as reactivity at the Se site toward C-based electrophiles.

Selenium-centered, undecanuclear silver cages surrounded by iodo and dialkyldiselenophosphato ligands. Syntheses, structures, and photophysical properties.

Three clusters [Ag11(mu9-Se)(mu3-I)3{Se2P(OR)2}6] (R = Et, 1; iPr, 2; 2Bu, 3) were isolated from the reaction of [Ag(CH3CN)4](PF6), NH4[Se2P(OR)2], and Bu4NI in a molar ratio of 4:3:1 in CH2Cl2 in 47-55% yield. Compounds 1 and 2 can also be synthesized with high yield from the reaction of Ag10(Se)[Se2P(OR)2]8 with 8 equiv of Bu4NI. In the positive fast atom bombardment mass spectra of 1-3, two major peaks that correspond to the intact molecule with the loss of an iodide ion, [Ag11(mu9-Se)(mu3-I)(2){Se2P(OR)2}6]+, and a diselenophosphate ligand, [Ag11(mu9-Se)(mu3-I)3{Se2P(OR)2}5]+, were identified.

Coordination chemistry of Group 12 metals with phosphorodiselenoates: syntheses, structures and VT 31P NMR study of monomer-dimer exchange equilibrium.

The reactions of diselenophosphates, [dsep, (RO)2PSe2-; R = Et, (n)Pr and (i)Pr] with cadmium(II) and mercury(II) perchlorates in a 2 : 1 molar ratio formed compounds of stoichiometry M[Se2P(OR)2]2{M = Cd, R = Et (1), (n)Pr (2), (i)Pr (3); Hg, Et(4), (n)Pr (5), (i)Pr (6)}, and with zinc(II) perchlorates, chalcogen centered tetranuclear clusters, [Zn4(micro4-E){Se2P(OR)2}6]{E = Se, R = Et (7), (n)Pr (8), (i)Pr (9); E = O, R = Et (10), (n)Pr (11), (i)Pr (12)} were formed. All these complexes have been characterized with the help of analytical data, X-ray crystallography (1, 3, 6, 10, 11 and 12), and FAB-mass spectrometry (7-12). Compound 1 is a linear double-chain polymer, in which each pair of Cd atoms is bridged by two dsep ligands; the mercury 6 polymer has a helical chain structure, in which two Hg atoms are bridged by one dsep ligand, and the other ligand chelates the Hg atom.

Versatility of dithiophosphates in the syntheses of copper(I) complexes with bis(diphenylphosphino)alkanes: abstraction of chloride from dichloromethane.

Reactions of [Cu(CH(3)CN)(4)]X (X = PF(6), BF(4)) with bis(diphenylphosphino)methane (dppm = Ph(2)PCH(2)PPh(2)) and ammonium dialkyldithiophosphates, (NH(4))[S(2)P(OR)(2)] (R = Et, (i)Pr), yield a series of novel Cu(I) polynuclear complexes, trinuclear [Cu(3)(mu-dppm)(3)(mu(3)-Cl){S(2)P(OEt)(2)}] (PF(6)) 1 and [Cu(3)(mu-dppm)(2){S(2)P(OR)(2)}(2)](PF(6)) (R = Et, 2; (i)Pr, 3), tetranuclear [Cu(4)(mu-dppm)(2) {S(2)P(OEt)(2)}(4)] 4, and hexanuclear [Cu(6)(mu-dppm)(2)(mu(4)-Cl){S(2)P(O(i)()Pr)(2)}(4)](BF(4)) 5. Similarly, the reaction of [Cu(2)(mu-L-L)(2)(CH(3)CN)(2)](PF(6))(2) (L-L, dppm, dppe = Ph(2)PCH(2)CH(2)PPh(2)) with (NH(4))[S(2)P(OR)(2)] yields dinuclear [Cu(2)(mu-dppm)(2){S(2)P(OR)(2)}(2)] 6 (R= (i)Pr, 6A; Et, 6B), trinuclear [Cu(3)(mu-dppe)(3)(mu-Cl)(2){S(2)P(O(i)Pr)(2)}] 9, and polymeric [Cu(mu(2)-dppe){S(2)P(OR)(2)}](n) (R = Et, 7; (i)Pr, 8) complexes. The formation of 1 and 5 involved the abstraction of chloride from dichloromethane when the Cu/S(2)P(OR)(2) ratio exceeded 1, but when ratio was 1:1, no Cl abstraction occurred, as in compound 4.

A 2D honeycomb-shaped network based on a starburst cluster: [Ag4(micro3-Cl)(PPh2(CH2)2PPh2)1.5{S2P(OR)2}3](R = Et, Pri).

The first 2D metal-organic framework utilizing PPh2(CH2)2PPh2 (dppe) units as the linkers and tetranuclear silver clusters, [Ag4(micro3)-Cl){S2P(OR)2}3], as the network nodes in the formation of the honeycomb-shaped layer structure is reported.

Linear and cyclic tetranuclear copper(I) complexes containing anions of N,N'-bis(pyrimidine-2-yl)formamidine.

The reaction of Kpmf (pmf = anion of N,N[prime or minute]-bis(pyrimidyl-2-yl)formamidine, Hpmf) with CuSCN afforded the complexes K[Cu4(pmF)3(SCN)2], 1, and Cu(4)(pmf)4, 2. Reaction of 1 with [(n-Bu)4N]PF6 in THF gave the complex [(n-Bu)4N][Cu4(pmf)3(SCN)2], 3. Their structures were characterized by X-ray crystallography.

The first, discrete Zn4 tetrahedron with a selenium atom in the center: x-ray structure and solution study of [Zn4(mu4-Se)[Se2P(OPr)2]6].

The first discrete, selenium-centered tetranuclear zinc cluster [Zn4(mu4-Se)[Se2P(OPr)2]6] was isolated and characterized. The cluster consists of six edge-bridged dsep ligands with four zinc atoms in a slightly distorted tetrahedron and a mu4-Se atom in the center. In addition, 12 mu2-bridging selenium atoms form a Se12 icosahedron.