Preparation and characterization of the argentates: [Ag[P(CF(3))(2)](2)](-), [Ag[(micro-P(CF(3))(2))M(CO)(5)](2)](-) (M = Cr, W), and [Ag[(micro-P(C(6)F(5))(2))W(CO)(5)](2)](-): X-ray crystal structure of [K(18-crown-6)][Ag[(micro-P(CF(3))(2))Cr(CO)(5)](2)

The first example of a mononuclear diphosphanidoargentate, bis[bis(trifluoromethyl)phosphanido]argentate, [Ag[P(CF(3))(2)](2)](-), is obtained via the reaction of HP(CF(3))(2) with [Ag(CN)(2)](-) and isolated as its [K(18-crown-6)] salt. When the cyclic phosphane (PCF(3))(4) is reacted with a slight excess of [K(18-crown-6)][Ag[P(CF(3))(2)](2)], selective insertion of one PCF(3) unit into each silver phosphorus bond is observed, which on the basis of NMR spectroscopic evidence suggests the [Ag[P(CF(3))P(CF(3))(2)](2)](-) ion. On treatment of the phosphane complexes [M(CO)(5)PH(CF(3))(2)] (M = Cr, W) with [K(18-crown-6)][Ag(CN)(2)], the analogous trinuclear argentates, [Ag[(micro-P(CF(3))(2))M(CO)(5)](2)](-), are formed. The chromium compound [K(18-crown-6)][Ag[(micro-P(CF(3))(2))Cr(CO)(5)](2)] crystallizes in a noncentrosymmetric space group Fdd2 (No. 43), a = 2970.2(6) pm, b = 1584.5(3) pm, c = 1787.0(4), V = 8.410(3) nm(3), Z = 8. The C(2) symmetric anion, [Ag[(micro-P(CF(3))(2))Cr(CO)(5)](2)](-), shows a nearly linear arrangement of the P-Ag-P unit. Although the bis(pentafluorophenyl)phosphanido compound [Ag[P(C(6)F(5))(2)](2)](-) has not been obtained so far, the synthesis of its trinuclear counterpart, [K(18-crown-6)][Ag[(micro-P(C(6)F(5))(2))W(CO)(5)](2)], was successful.     

Designed synthesis of metal cluster-centered pseudo-rotaxane supramolecular architectures

The designed synthesis and structural characterization of two metal cluster-centered metallosupramolecular architectures are reported. In complex [(CF(3)SO(3))Ag(4)((t)BuC≡C)(Py8)](CF(3)SO(3))(2) (1) and [(CF(3)SO(3))Ag(4){C≡C-(m-C(6)H(4))-C≡C-(m-C(6)H(4))-C≡C-(m-C(6)H(4))-C≡C}Ag(4)(CF(3)SO(3))(Py8)(2)](CF(3)SO(3))(4) (2), organic acetylide ligands are utilized to induce the formation of polynuclear silver aggregates, which are encapsulated into the central cavity of the neutral macrocyclic compound azacalix[8]pyridine (Py8). The tetrasilver cluster centered [2]- and [3]-pseudo-rotaxane structures are obtained and fully characterized by X-ray crystallography, ESI mass spectrometry, and (1)H NMR spectroscopy.     

Assembly of discrete,one-, two-, and three-dimensional silver(I) supramolecular complexes containing encapsulated acetylide dianion with nitrogen-donor spacers

The first successful attempt to construct supramolecular entities via incorporation of bifunctional exodentate ligands into the silver acetylide system is reported. Coordination assembly with nitrogen-donor spacers led to the formation of five distinct supramolecular complexes, namely [(Ag(2)C(2))(AgCF(3)CO(2))(4)(pyz)(2)](n) (1), [(Ag(2)C(2))(2)(AgCF(3)CO(2))(10)(CF(3)CO(2))(4)(DabcoH)(4)(H(2)O)(1.5)].H(2)O (2), [(Ag(2)C(2))(AgCF(3)CO(2))(4)(CF(3)CO(2))(bpaH)](n)() (3), [(Ag(2)C(2))(AgCF(3)CO(2))(8)(bpa)(4)](n) (4), and [(Ag(2)C(2))(2)(AgCF(3)CO(2))(10)(bppz)(2)(H(2)O)](n) (5) (pyz = pyrazine; Dabco = 1,4-diazabicyclo[2.2.2]octane; bpa = 1,2-bis(4-pyridyl)ethane; bppz = 2,3-bis(2-pyridyl)pyrazine). Complex 1 is a three-dimensional framework composed of silver columns cross-linked by pyrazine bridges, whereas 2 contains a discrete supermolecule whose core is a Ag(14) double cage that is completely surrounded by trifluoroacetate, aqua, and terminal monoprotonated Dabco ligands. Complex 3 has a branched-tree architecture with one terminal of the bpa ligand attached to the silver backbone and the other exposed and protonated. In 4, neutral decanuclear [(Ag(2)C(2))(AgCF(3)CO(2))(8)] units are interlinked by bpa spacers adopting both gauche and anti conformations to generate a layer structure. Another two-dimensional network was formed with bppz serving as an angular bridging ligand in 5, in which the building unit is a silver quadruple cage containing 24 silver atoms.     

Crown ethers as ancillary ligands in the assembly of silver(i) aggregates containing embedded acetylenediide

Five silver(I) double salts containing embedded acetylenediide, [Ag([12]crown-4)(2)][Ag(10)(C(2))(CF(3)CO(2))(9)([12]crown-4)(2)(H(2)O)(3)] x H(2)O (2), [Ag(2)C(2) x 5 AgCF(3)CO(2) x (benzo[15]crown-5) x 2 H(2)O] x 0.5 H(2)O (3), [Ag(4)([18]crown-6)(4)(H(2)O)(3)][Ag(18)(C(2))(3)(CF(3)CO(2))(16)(H(2)O)(2.5)] x 2.5 H(2)O (4), [Ag(2)C(2) x 6 AgC(2)F(5)CO(2) x 2([15]crown-5)](2) (5), and [(Ag(2)C(2))(2) x (AgC(2)F(5)CO(2))(9) x ([18]crown-6)(2) x (H(2)O)(3.5)] x H(2)O (6), have been isolated by varying the types of crown ethers and anions employed. Single-crystal X-ray analysis has shown that complex 2 is composed of winding anionic chains with sandwiched [Ag([12]crown-4)(2)](+) ions accommodated in the concave cavities between them. In 3, silver(I) double cages each sandwiched by a couple of benzo[15]crown-5 ligands are linked by [Ag(2)(CF(3)CO(2))(2)] bridges to form a one-dimensional structure. For 4, an anionic silver column is generated through fusion of two kinds of silver polyhedra (triangulated dodecahedron and bicapped trigonal antiprism), and the charge balance is provided by aqua-ligated [Ag([18]crown-6)](+) ions. Complex 5 is a centrosymmetric hexadecanuclear supermolecule composed of two [(eta(5)-[15]crown-5)(2)(C(2)@Ag(7))(mu-C(2)F(5)CO(2))(5)] moieties connected through a [Ag(2)(C(2)F(5)CO(2))(2)] bridge. Compound 6 is a discrete supermolecule containing an asymmetric (C(2))(2)@Ag(13) cluster core capped by two [18]crown-6 ligands in mu(3)-eta(5) and mu(4)-eta(6) ligation modes.     

Silver(I)-organophosphane complexes of electron withdrawing CF3- or NO2-substituted scorpionate ligands

New silver(I) complexes have been synthesized from the reaction of AgNO(3), monodentate tertiary phosphanes PR(3) (PR(3) = P(C(6)H(5))(3), P(o-C(6)H(4)CH(3))(3), P(m-C(6)H(4)CH(3))(3), P(p-C(6)H(4)CH(3))(3), PCH(3)(C(6)H(5))(2)) and two novel electron withdrawing ligands: potassium dihydrobis(3-nitropyrazol-1-yl)borate and potassium dihydrobis(3-trifluoromethylpyrazol-1-yl)borate. These compounds have been characterized by elemental analyses, FT-IR, ESI-MS and multinuclear ((1)H, (19)F and (31)P) NMR spectroscopy. Solid state structures of the potassium salts K[H(2)B(3-(NO(2))pz)(2)] and K[H(2)B(3-(CF(3))pz)(2)] have been reported. They form polymeric networks due to intermolecular contacts of various types between the potassium ion and atoms of the neighboring molecules. The silver adducts [H(2)B(3-(NO(2))pz)(2)]Ag[P(C(6)H(5))(3)](2) and [H(2)B(3-(NO(2))pz)(2)]Ag[P(p-C(6)H(4)CH(3))(3)] have pseudo tetrahedral and trigonal planar silver sites, respectively. The bis(pyrazolyl)borate ligand acts as a kappa(2)-N(2) donor. The nitro-substituents are coplanar with the pyrazolyl rings in all these adducts indicating efficient electron delocalization between the two units. The [H(2)B(3-(CF(3))pz)(2)]Ag[P(C(6)H(5))(3)] complex has been obtained from re-crystallization of {[H(2)B(3-(CF(3))pz)(2)]Ag[P(C(6)H(5))(3)](2)} in a dichloromethane-diethyl ether solution; it is a three-coordinate, trigonal planar silver complex.     

Acceptor (CF3)PCPH pincer reactivity with (PPh3)3Ir(CO)H

The syntheses of Ir(I) and Ir(III) complexes incorporating the electron-withdrawing pincer ligand (1,3-C(6)H(4)(CH(2)P(CF(3))(2))(2)) ((CF(3))PCPH) with (PPh(3))(3)Ir(CO)H and subsequent chemistry are reported. Under ambient conditions, reaction of 1 equiv. (CF(3))PCPH with (PPh(3))(3)Ir(CO)H gave the mono-bridged complex [Ir(CO)(PPh(3))(2)(H)](2)(μ-(CF(3))PCPH) (1). Reaction of (PPh(3))(3)Ir(CO)H with excess (CF(3))PCPH and MeI gave the doubly-bridged complex [Ir(CO)(PPh(3))(H)](2)(μ-(CF(3))PCPH)(2) (2), whereas the tetrameric oligomer [Ir(CO)(PPh(3))(H)](4)(μ-(CF(3))PCPH)(4) (2-sq) was obtained from a 1:1 ligand:metal mixture in benzene in the presence of excess MeI. At higher temperatures (165 °C) the reaction of (CF(3))PCPH with (PPh(3))(3)Ir(CO)H afforded the 5-coordinate Ir(I) complex ((CF(3))PCP)Ir(CO)(PPh(3)) (3). Complex 3 shows mild catalytic activity for the decarbonylation of 2-naphthaldehyde in refluxing diglyme (162 °C).     

New family of silver(I) complexes based on hydroxyl and carboxyl groups decorated arenesulfonic acid: syntheses, structures, and luminescent properties

Self-assembly of silver(I) salts and three ortho-hydroxyl and carboxyl groups decorated arenesulfonic acids affords the formation of nine silver(I)-sulfonates, (NH(4))·[Ag(HL1)(NH(3))(H(2)O)] (1), {(NH(4))·[Ag(3)(HL1)(2)(NH(3))(H(2)O)]}(n) (2), [Ag(2)(HL1)(H(2)O)(2)](n) (3), [Ag(2)(HL2)(NH(3))(2)]·H(2)O (4), [Ag(H(2)L2)(H(2)O)](n) (5), [Ag(2)(HL2)](n) (6), [Ag(3)(L3)(NH(3))(3)](n) (7), [Ag(2)(HL3)](n) (8), and [Ag(6)(L3)(2)(H(2)O)(3)](n) (9) (H(3)L1 = 2-hydroxyl-3-carboxyl-5-bromobenzenesulfonic acid, H(3)L2 = 2-hydroxyl-4-carboxylbenzenesulfonic acid, H(3)L3 = 2-hydroxyl-5-carboxylbenzenesulfonic acid), which are characterized by elemental analysis, IR, TGA, PL, and single-crystal X-ray diffraction. Complex 1 is 3-D supramolecular network extended by [Ag(HL1)(NH(3))(H(2)O)](-) anions and NH(4)(+) cations. Complex 2 exhibits 3-D host-guest framework which encapsulates ammonium cations as guests. Complex 3 presents 2-D layer structure constructed from 1-D tape of sulfonate-bridged Ag1 dimers linked by [(Ag2)(2)(COO)(2)] binuclear units. Complex 4 exhibits 3-D hydrogen-bonding host-guest network which encapsulates water molecules as guests. Complex 5 shows 3-D hybrid framework constructed from organic linker bridged 1-D Ag-O-S chains while complex 6 is 3-D pillared layered framework with the inorganic substructure constructing from the Ag2 polyhedral chains interlinked by Ag1 dimers and sulfonate tetrahedra. The hybrid 3-D framework of complex 7 is formed by L3(-) trianions bridging short trisilver(I) sticks and silver(I) chains. Complex 8 also presents 3-D pillared layered framework, and the inorganic layer substructure is formed by the sulfonate tetrahedrons bridging [(Ag1O(4))(2)(Ag2O(5))(2)](∞) motifs. Complex 9 represents the first silver-based metal-polyhedral framework containing four kinds of coordination spheres with low coordination numbers. The structural diversities and evolutions can be attributed to the synthetic methods, different ligands and coordination modes of the three functional groups, that is, sulfonate, hydroxyl and carboxyl groups. The luminescent properties of the nine complexes have also been investigated at room temperature, especially, complex 1 presents excellent blue luminescence and can sensitize Tb(III) ion to exhibit characteristic green emission.     

Metastable Se6 as a ligand for Ag+: from isolated molecular to polymeric 1D and 2D structures

Attempts to prepare the hitherto unknown Se(6)(2+) cation by the reaction of elemental selenium and Ag[A] ([A](-) = [Sb(OTeF(5))(6)](-), [Al(OC(CF(3))(3))(4)](-)) in SO(2) led to the formation of [(OSO)Ag(Se(6))Ag(OSO)][Sb(OTeF(5))(6)](2)1 and [(OSO)(2)Ag(Se(6))Ag(OSO)(2)][Al(OC(CF(3))(3))(4)](2)2a. 1 could only be prepared by using bromine as co-oxidant, however, bulk 2b (2a with loss of SO(2)) was accessible from Ag[Al(OC(CF(3))(3))(4)] and grey Se in SO(2) (chem. analysis). The reactions of Ag[MF(6)] (M = As, Sb) and elemental selenium led to crystals of 1/∞{[Ag(Se(6))](∞)[Ag(2)(SbF(6))(3)](∞)} 3 and {1/∞[Ag(Se(6))Ag](∞)}[AsF(6)](2)4. Pure bulk 4 was best prepared by the reaction of Se(4)[AsF(6)](2), silver metal and elemental selenium. Attempts to prepare bulk 1 and 3 were unsuccessful. 1-4 were characterized by single-crystal X-ray structure determinations, 2b and 4 additionally by chemical analysis and 4 also by X-ray powder diffraction, FT-Raman and FT-IR spectroscopy. Application of the PRESTO III sequence allowed for the first time (109)Ag MAS NMR investigations of 4 as well as AgF, AgF(2), AgMF(6) and {1/∞[Ag(I(2))](∞)}[MF(6)] (M = As, Sb). Compounds 1 and 2a/b, with the very large counter ions, contain isolated [Ag(Se(6))Ag](2+) heterocubane units consisting of a Se(6) molecule bicapped by two silver cations (local D(3d) sym). 3 and 4, with the smaller anions, contain close packed stacked arrays of Se(6) rings with Ag(+) residing in octahedral holes. Each Ag(+) ion coordinates to three selenium atoms of each adjacent Se(6) ring. 4 contains [Ag(Se(6))(+)](∞) stacks additionally linked by Ag(2)(+) into a two dimensional network. 3 features a remarkable 3-dimensional [Ag(2)(SbF(6))(3)](-) anion held together by strong Sb-FAg contacts between the component Ag(+) and [SbF(6)](-) ions. The hexagonal channels formed by the [Ag(2)(SbF(6))(3)](-) anions are filled by stacks of [Ag(Se(6))(+)](∞) cations. Overall 1-4 are new members of the rare class of metal complexes of neutral main group elemental clusters, in which the main group element is positively polarized due to coordination to a metal ion. Notably, 1 to 4 include the commonly metastable Se(6) molecule as a ligand. The structure, bonding and thermodynamics of 1 to 4 were investigated with the help of quantum chemical calculations (PBE0/TZVPP and (RI-)MP2/TZVPP, in part including COSMO solvation) and Born-Fajans-Haber-cycle calculations. From an analysis of all the available data it appears that the formation of the usually metastable Se(6) molecule from grey selenium is thermodynamically driven by the coordination to the Ag(+) ions.     

Luminescent Ag i-Cu i heterometallic hexa-, octa-, and hexadecanuclear alkynyl complexes

A series of Ag(I)-Cu(I) heteronuclear alkynyl complexes were prepared by reaction of polymeric (MCCC(6)H(4)R-4)(n)() (M = Cu(I) or Ag(I); R = H, CH(3), OCH(3), NO(2), COCH(3)) with [M'(2)(mu-Ph(2)PXPPh(2))(2)(MeCN)(2)](ClO(4))(2) (M' = Ag(I) or Cu(I); X = NH or CH(2)). Heterohexanuclear complexes [Ag(4)Cu(2)(mu-Ph(2)PNHPPh(2))(4)(CCC(6)H(4)R-4)(4)](ClO(4))(2) (R = H, 1; CH(3), 2) were afforded when X = NH, and heterooctanuclear complexes [Ag(6)Cu(2)(micro-Ph(2)PCH(2)PPh(2))(3)(CCC(6)H(4)R-4)(6)(MeCN)](ClO(4))(2) (R = H, 3; CH(3), 4; OCH(3), 5; NO(2), 6) were isolated when X = CH(2). Self-assembly reaction between (MCCC(6)H(4)COCH(3)-4)(n) and [M'(2)(mu-Ph(2)PCH(2)PPh(2))(2)(MeCN)(2)](ClO(4))(2), however, gave heterohexadecanuclear complex [Ag(6)Cu(2)(micro-Ph(2)PCH(2)PPh(2))(3)(CCC(6)H(4)COCH(3)-4)(6)](2)(ClO(4))(4) (7). The heterohexanuclear complexes 1 and 2 show a bicapped cubic skeleton (Ag(4)Cu(2)C(4)) consisting of four Ag(I) and two Cu(I) atoms and four acetylide C donors. The heterooctanuclear complexes 3-6 exhibit a waterwheel-like structure that can be regarded as two Ag(3)Cu(CCC(6)H(5))(3) components put together by three bridging Ph(2)PCH(2)PPh(2) ligands. The heterohexadecanuclear complex 7 can be viewed as a dimer of heterooctanuclear complex [Ag(6)Cu(2)(micro-Ph(2)PCH(2)PPh(2))(3)(CCC(6)H(4)COCH(3)-4)(6)](ClO(4))(2) through the silver and acetyl oxygen (Ag-O = 2.534 (4) A) linkage between two waterwheel-like Ag(6)Cu(2) units. All of the complexes show intense luminescence in the solid states and in fluid solutions. The microsecond scale of lifetimes in the solid state at 298 K reveals that the emission is phosphorescent in nature. The emissive state in compounds 1-5 is likely derived from a (3)LMCT (CCC(6)H(4)R-4 --> Ag(4)Cu(2) or Ag(6)Cu(2)) transition, mixed with a metal cluster-centered (d --> s) excited state. The lowest lying excited state in compounds 6 and 7 containing electron-deficient 4-nitrophenylacetylide and 4-acetylphenylacetylide, respectively, however, is likely dominated by an intraligand (3)[pi --> pi] character.     

Construction of the multidecker anthracene-silver(I) system by intramolecular pi-pi interactions

As a continuation of the study on the construction of the multidecker aromatic compounds with pi-pi interactions, the anthracene derivatives 9,10-dimethylanthracene (dman), 9,10-diphenylanthracene (dpan), and 7,12-dimethylbenz[a]anthracene (dmban) have been studied toward complexation with the silver(I) ion. The crystal structures of [Ag(dman)(0.5)(p-xylene)(ClO(4))], [Ag(2)(dpan)(0.5)(C(6)H(6))(0.5)(CF(3)SO(3))(2)], and [Ag(2)(dmban)(2)(ClO(4))(2)](p-xylene), together with the metal-free ligand dpan, have been determined by single-crystal X-ray diffraction. These pi-electron-rich aromatic compounds are found to have great promise as an approach to the effective self-assembly of high nuclearity in a multilayer fashion.     

Preparation and characterization of [Hg[P(C6F5)2]2], [Hg[(mu-P(C6F5)2)W(CO)5]2], and [Hg[(mu-P(CF3)2)W(CO)5]2] and the X-ray crystal structure of [Hg[(mu-P(C6F5)2)W(CO)5]2].2DMF

The thermally unstable compound [Hg[P(C(6)F(5))(2)](2)] was obtained from the reaction of mercury cyanide and bis(pentafluorophenyl)phosphane in DMF solution and characterized by multinuclear NMR spectroscopy. The thermally stable trinuclear compounds [Hg[(mu-P(CF(3))(2))W(CO)(5)](2)] and [Hg[(mu-P(C(6)F(5))(2))W(CO)(5)](2)] are isolated and completely characterized. The higher order NMR spectra exhibiting multinuclear satellite systems have been sufficiently analyzed. [Hg[(mu-P(CF(3))(2))W(CO)(5)](2)].2DMF crystallizes in the monoclinic space group C2/c with a = 2366.2(3) pm, b = 1046.9(1) pm, c = 104.0(1) pm, and beta = 104.01(1) degrees. Structural, NMR spectroscopic, and vibrational data prove a weak coordination of the two DMF molecules. Structural, vibrational, and NMR spectroscopic evidence is given for a successive weakening of the pi back-bonding effect of the W-P bond in the order [W(CO)(5)PH(R(f))(2)], [Hg[(mu-P(R(f))(2))W(CO)(5)](2)], and [W[P(R(f))(2)](CO)(5)](-) with R(f) = C(6)F(5) and CF(3). The pi back-bonding effect of the W-C bonds increases vice versa.     

Synthesis, characterization, crystal structure and preliminary reactivity behaviour of new heteropolytopic ligands based on the 1,3,5-triazine spacer and pyrazolyl, tris-pyrazolylmethyl and tris-pyrazolylethoxy bonding fragments

Four new potentially polytopic nitrogen donor ligands based on the 1,3,5-triazine fragment, L(1)-L(4) (L(1) = 2-chloro-4,6-di(1H-pyrazol-1-yl)-1,3,5-triazine, L(2) = N,N'-bis(4,6-di(1H-pyrazol-1-yl)-1,3,5-triazin-2-yl)ethane-1,2-diamine, L(3) = 2,4,6-tris(tri(1H-pyrazol-1-yl)methyl)-1,3,5-triazine, and L(4) = 2,4,6-tris(2,2,2-tri(1H-pyrazol-1-yl)ethoxy)-1,3,5-triazine) have been synthesized and characterized. The X-ray crystal structure of L(3) confirms that its molecular nature consists of a 1,3,5-triazine ring bearing three tripodal tris(pyrazolyl) arms. L(1), L(2), and L(4) react with Cu(I), Cu(II), Pd(II) and Ag(I) salts yielding mono-, di-, and oligonuclear derivatives: [Cu(L(1))(Cy(3)P)]ClO(4), [{Ag(2)(L(2))}(CF(3)SO(3))(2)]·H(2)O, [Cu(2)(L(2))(NO(3))(2)](NO(3))(2)·H(2)O, [Cu(2)(L(2))(CH(3)COO)(2)](CH(3)COO)(2)·3H(2)O, [Pd(2)(L(2))(Cl)(4)]·2H(2)O, [Ru(L(2))(Cl)(OH)]·CH(3)OH, [Ag(3)(L(4))(2)](CF(3)SO(3))(3) and [Ag(3)(L(4))(2)](BF(4))(3). The interaction of L(3) with Ag(I), Cu(II), Zn(II) and Ru(II) complexes unexpectedly produced the hydrolysis of the ligand with formation, in all cases, of tris(pyrazolyl)methane (TPM) derivatives. In detail, the already known [Ag(TPM)(2)](CF(3)SO(3)) and [Cu(TPM)(2)](NO(3))(2), as well as the new [Zn(TPM)(2)](CF(3)SO(3))(2) and [Ru(TMP)(p-cymene)]Cl(OH)·2H(2)O complexes have been isolated. Single-crystal XRD determinations on the latter derivatives confirm their formulation, evidencing, for the Ru(II) complex, an interesting supramolecular arrangement of the anions and crystallization water molecules.     

Self-assembled silver polyhedra with embedded acetylide dianion stabilized by perfluorocarboxylate and 4-hydroxyquinoline ligands

Four new silver(I) double salts (L(2)H)(4)[Ag(10)(C(2))(CF(3)CO(2))(12)(L)(2)].5H(2)O (1), [Ag(8)(C(2))(CF(3)CO(2))(6)(L)(6)] (2), [(Ag(2)C(2))(AgC(2)F(5)CO(2))(6)(L)(3)(H(2)O)].H(2)O (3), and (L.H(3)O)(2)[Ag(11)(C(2))(2)(C(2)F(5)CO(2))(9)(H(2)O)(2)].H(2)O (4) incorporating the hitherto unexplored ligand 4-hydroxyquinoline (L) have been synthesized by the hydrothermal method. Compound 1 features an unprecedented bicapped square-antiprismatic Ag(10) silver cage with an embedded C(2)(2-) moiety, whereas the discrete supermolecule 2 bears a rhombohedral Ag(8) core similar to that previously found in Ag(2)C(2).6AgNO(3). Compound 3 contains a discrete supramolecular complex whose core is a (C(2))(2)@Ag(16) double cage constructed from the edge-sharing of two monocapped square antiprisms, which is completely surrounded by 12 pentafluoropropionate, 6 4-hydroxyquinoline, and 2 aqua ligands. The layer structure in 4 is constructed from a sinuous anionic silver column composed of fused irregular monocapped trigonal antiprisms each encapsulating a C(2)(2-) dianion, with L.H(3)O(+) species serving as hydrogen-bond connectors to adjacent columns.     

Synthesis, structure and reactivity of novel pyridazine-coordinated diiron bridging carbene complexes

[{mu-(Pyridazine-N(1):N(2))}Fe(2)(mu-CO)(CO)(6)](1) reacts with aryllithium reagents, ArLi (Ar = C(6)H(5), m-CH(3)C(6)H(4)) followed by treatment with Me(3)SiCl to give the novel pyridazine-coordinated diiron bridging siloxycarbene complexes [(C(4)H(4)N(2))Fe(2){mu-C(OSiMe(3))Ar}(CO)(6)](2, Ar = C(6)H(5); 3, Ar =m-CH(3)C(6)H(4)). Complex 2 reacts with HBF(4).Et(2)O at low temperature to yield a cationic bridging carbyne complex [(C(4)H(4)N(2))Fe(2)(mu-CC(6)H(5))(CO)(6)]BF(4)(4). Cationic 4 reacts with NaBH(4) in THF at low temperature to afford the diiron bridging arylcarbene complex [(C(4)H(4)N(2))Fe(2){mu-C(H)C(6)H(5)}(CO)(6)](5). Unexpectedly, the reaction of 4 with NaSCH(3) under similar conditions gave the bridging arylcarbene complex 5 and a carbonyl-coordinated diiron bridging carbene complex [Fe(2){mu-C(SCH(3))C(6)H(5)}(CO)(7)](6), while the reaction of NaSC(6)H(4)CH(3)-p with 4 affords the expected bridging arylthiocarbene complex [(C(4)H(4)N(2))Fe(2){mu-C(SC(6)H(4)CH(3)-p)C(6)H(5)}(CO)(6)](7), which can be converted into a novel diiron bridging carbyne complex with a thiolato-bridged ligand, [Fe(2)(mu-CC(6)H(5))(mu-SC(6)H(4)CH(3)-p)(CO)(6)](8). Cationic can also react with the carbonylmetal anionic compound Na(2)[Fe(CO)(4)] to yield complex 5, while the reactions of 4 with carbonylmetal anionic compounds Na[M(CO)(5)(CN)](M = Cr, Mo, W) produce the diiron bridging aryl(pentacarbonylcyanometal)carbene complexes [(C(4)H(4)N(2))Fe(2)-{mu-C(C(6)H(5))NCM(CO)(5)}(CO)(6)](9, M = Cr; 10, M = Mo; 11, M = W). The structures of complexes 2, 5, 6, 8, and 9 have been established by X-ray diffraction studies.     

Silver(I)-ethynide clusters constructed with phosphonate-functionized polyoxovanadates

Two neutral silver(I)-phenylethynide clusters incorporating the [((t)BuPO(3))(4)V(4)O(8)](4-) unit as an integral shell component, namely {(NO(3))(2)@Ag(16)(C≡CPh)(4)[((t)BuPO(3))(4)V(4)O(8)](2)(DMF)(6)(NO(3))(2)}·DMF·H(2)O and {[(O(2))V(2)O(6)](3)@Ag(43)(C≡CPh)(19)[((t)BuPO(3))(4)V(4)O(8)](3)(DMF)(6)}·5DMF·2H(2)O, have been isolated and characterized by X-ray crystallography. The central cavities of the Ag(16) and Ag(43) clusters are occupied by two NO(3)(-) and three [(O(2))V(2)O(6)](4-) template anions, respectively.     

Synthesis, reactivity, electrochemical behavior, and crystal structure of a family of multivalent metal carbido-carbonyl clusters based on the rh(10)(c)(2)au(4-6) framework

Six metal carbido-carbonyl clusters have been isolated and recognized as members of a multivalent family based on the dioctahedral Rh(10)(C)(2) frame, with variable numbers of CO ligands, AuPPh(3) moieties, and anionic charge: [Rh(10)(C)(2)(CO)(x)(AuPPh(3))(y)](n-) (x = 18, 20; y = 4, 5, 6; n = 0, 1, 2). Anions [Rh(10)(C)(2)(CO)(18)(AuPPh(3))(4)](-) ([2](-)) and [Rh(10)(C)(2)(CO)(18)(AuPPh(3))(4)](2-) ([2](2-)) have been obtained by the reduction of [Rh(10)(C)(2)(CO)(18)(AuPPh(3))(4)] (2) under N(2), while [Rh(10)(C)(2)(CO)(18)(AuPPh(3))(5)](-) ([3](-)) was obtained from [Rh(10)(C)(2)(CO)(20)(AuPPh(3))(4)] (1) by reduction under a CO atmosphere. [3](-) can be better obtained by the addition of AuPPh(3)Cl to [2](2-). [Rh(10)(C)(2)(CO)(18)(AuPPh(3))(6)] (4) is obtained from [3](-) and 2 as well by the reduction and subsequent addition of AuPPh(3)Cl. The molecular structures of [2](2-) ([NBu(4)](+) salt), [3](-) ([NMe(4)](+) salt), and 4 have been determined by single-crystal X-ray diffraction. The redox activities of complexes 1, 2 and [3](-) have been investigated by electrochemical and electron paramagnetic resonance (EPR) techniques. The data from EPR spectroscopy have been accounted for by theoretical calculations.     

Alkynyldiphenylphosphine d8 (Pt, Rh, Ir) complexes: contrasting behavior toward cis-[Pt(C6F5)2(THF)2

The synthesis and characterization of a series of mononuclear d(8) complexes with at least two P-coordinated alkynylphosphine ligands and their reactivity toward cis-[Pt(C(6)F(5))(2)(THF)(2)] are reported. The cationic [Pt(C(6)F(5))(PPh(2)C triple-bond CPh)(3)](CF(3)SO(3)), 1, [M(COD)(PPh(2)C triple-bond CPh)(2)](ClO(4)) (M = Rh, 2, and Ir, 3), and neutral [Pt(o-C(6)H(4)E(2))(PPh(2)C triple-bond CPh)(2)] (E = O, 6, and S, 7) complexes have been prepared, and the crystal structures of 1, 2, and 7.CH(3)COCH(3) have been determined by X-ray crystallography. The course of the reactions of the mononuclear complexes 1-3, 6, and 7 with cis-[Pt(C(6)F(5))(2)(THF)(2)] is strongly influenced by the metal and the ligands. Thus, treatment of 1 with 1 equiv of cis-[Pt(C(6)F(5))(2)(THF)(2)] gives the double inserted cationic product [Pt(C(6)F(5))(S)mu-(C(Ph)=C(PPh(2))C(PPh(2))=C(Ph)(C(6)F(5)))Pt(C(6)F(5))(PPh(2)C triple-bond CPh)](CF(3)SO(3)) (S = THF, H(2)O), 8 (S = H(2)O, X-ray), which evolves in solution to the mononuclear complex [(C(6)F(5))(PPh(2)C triple-bond CPh)Pt(C(10)H(4)-1-C(6)F(5)-4-Ph-2,3-kappaPP'(PPh(2))(2))](CF(3) SO(3)), 9 (X-ray), containing a 1-pentafluorophenyl-2,3-bis(diphenylphosphine)-4-phenylnaphthalene ligand, formed by annulation of a phenyl group and loss of the Pt(C(6)F(5)) unit. However, analogous reactions using 2 or 3 as precursors afford mixtures of complexes, from which we have characterized by X-ray crystallography the alkynylphosphine oxide compound [(C(6)F(5))(2)Pt(mu-kappaO:eta(2)-PPh(2)(O)C triple-bond CPh)](2), 10, in the reaction with the iridium complex (3). Complexes 6 and 7, which contain additional potential bridging donor atoms (O, S), react with cis-[Pt(C(6)F(5))(2)(THF)(2)] in the appropriate molar ratio (1:1 or 1:2) to give homo- bi- or trinuclear [Pt(PPh(2)C triple-bond CPh)(mu-kappaE-o-C(6)H(4)E(2))(mu-kappaP:eta(2)-PPh(2)C triple-bond CPh)Pt(C(6)F(5))(2)] (E = O, 11, and S, 12) and [(Pt(mu(3)-kappa(2)EE'-o-C(6)H(4)E(2))(mu-kappaP:eta(2)-PPh(2)C triple-bond CPh)(2))(Pt(C(6)F(5))(2))(2)] (E = O, 13, and S, 14) complexes. The molecular structure of 14 has been confirmed by X-ray diffraction, and the cyclic voltammetric behavior of precursor complexes 6 and 7 and polymetallic derivatives 11-14 has been examined.     

Coupling of CpCr(CO)3 and heterocyclic dithiadiazolyl radicals. synthetic, x-ray diffraction, dynamic NMR, EPR, CV, and DFT studies

The reaction of the 1,2,3,5-dithiadiazolyls (4-R-C(6)H(4)CN(2)S(2))(2) (R = Me, 2a; Cl, 2b; OMe, 2c; and CF3, 2d) and (3-NC-5-tBu-C(6)H(3)CN(2)S(2))(2) (2e) with [CpCr(CO)(3)](2) (Cp = eta(5)-C(5)H(5)) (1) at ambient temperature respectively yielded the complexes CpCr(CO)(2)(eta(2)-S(2)N(2)CC(6)H(4)R) (R = 4-Me, 3a; 4-Cl, 3b; 4-OMe, 3c; and 4-CF(3), 3d) and CpCr(CO)(2)(eta(2)-S(2)N(2)CC(6)H(3)-3-(CN)-5-(tBu)) (3e) in 35-72% yields. The complexes 3c and 3d were also synthesized via a salt metathesis method from the reaction of NaCpCr(CO)(3) (1B) and the 1,2,3,5-dithiadiazolium chlorides 4-R-C(60H(4)CN(2)S(2)Cl (R = OMe, 8c; CF(3), 8d) with much lower yields of 6 and 20%, respectively. The complexes were characterized spectroscopically and also by single-crystal X-ray diffraction analysis. Cyclic voltammetry experiments were conducted on 3a-e, EPR spectra were obtained of one-electron-reduced forms of 3a-e, and variable temperature 1H NMR studies were carried out on complex 3d. Hybrid DFT calculations were performed on the model system [CpCr(CO)(2)S(2)N(2)CH] and comparisons are made with the reported CpCr(CO)(2)(pi-allyl) complexes.     

Formation and chemical reactivities of a new type of double-butterfly [[Fe2(mu-CO)(CO)6]2(mu-SZS-mu)]2-: synthetic and structural studies on novel linear and macrocyclic butterfly Fe/E (E=S,Se) cluster complexes

A new type of double-butterfly [[Fe(2)(mu-CO)(CO)(6)](2)(mu-SZS-mu)](2-) (3), a dianion that has two mu-CO ligands, has been synthesized from dithiol HSZSH (Z=(CH(2))(4), CH(2)(CH(2)OCH(2))(1-3)CH(2)), [Fe(3)(CO)(12)], and Et(3)N in a molar ratio of 1:2:2 at room temperature. Interestingly, the in situ reactions of dianions 3 with various electrophiles affords a series of novel linear and macrocyclic butterfly Fe/E (E=S, Se) cluster complexes. For instance, while reactions of 3 with PhC(O)Cl and Ph(2)PCl give linear clusters [[Fe(2)(mu-PhCO)(CO)(6)](2)(mu-SZS-mu)] (4 a,b: Z=CH(2)(CH(2)OCH(2))(2,3)CH(2)) and [[Fe(2)(mu-Ph(2)P)(CO)(6)](2)(mu-SZS-mu)] (5 a,b: Z=CH(2)(CH(2)OCH(2))(2,3)CH(2)), reactions with CS(2) followed by treatment with monohalides RX or dihalides X-Y-X give both linear clusters [[Fe(2)(mu-RCS(2))(CO)(6)](2)(mu-SZS-mu)] (6 a-e: Z=CH(2)(CH(2)OCH(2))(1,2)CH(2); R=Me, PhCH(2), FeCp(CO)(2)) and macrocyclic clusters [[Fe(2)(CO)(6)](2)(mu-SZS-mu)(mu-CS(2)YCS(2)-mu)] (7 a-e: Z=(CH(2))(4), CH(2)(CH(2)OCH(2))(1-3)CH(2); Y=(CH(2))(2-4), 1,3,5-Me(CH(2))(2)C(6)H(3), 1,4-(CH(2))(2)C(6)H(4)). In addition, reactions of dianions 3 with [Fe(2)(mu-S(2))(CO)(6)] followed by treatment with RX or X-Y-X give linear clusters [[[Fe(2)(CO)(6)](2)(mu-RS)(mu(4)-S)](2)(mu-SZS-mu)] (8 a-c: Z=CH(2)(CH(2)OCH(2))(1,2)CH(2); R=Me, PhCH(2)) and macrocyclic clusters [[[Fe(2)(CO)(6)](2)(mu(4)-S)](2)(mu-SYS-mu)(mu-SZS-mu)] (9 a,b: Z=CH(2)(CH(2)OCH(2))(2,3)CH(2); Y=(CH(2))(4)), and reactions with SeCl(2) afford macrocycles [[Fe(2)(CO)(6)](2)(mu(4)-Se)(mu-SZS-mu)] (10 d: Z=CH(2)(CH(2)OCH(2))(3)CH(2)) and [[[Fe(2)(CO)(6)](2)(mu(4)-Se)](2)(mu-SZS-mu)(2)] (11 a-d: Z=(CH(2))(4), CH(2)(CH(2)OCH(2))(1-3)CH(2)). Production pathways have been suggested; these involve initial nucleophilic attacks by the Fe-centered dianions 3 at the corresponding electrophiles. All the products are new and have been characterized by combustion analysis and spectroscopy, and by X-ray diffraction techniques for 6 c, 7 d, 9 b, 10 d, and 11 c in particular. X-ray diffraction analyses revealed that the double-butterfly cluster core Fe(4)S(2)Se in 10 d is severely distorted in comparison to that in 11 c. In view of the Z chains in 10 a-c being shorter than the chain in 10 d, the double cluster core Fe(4)S(2)Se in 10 a-c would be expected to be even more severely distorted, a possible reason for why 10 a-c could not be formed.     

Polyfluorinated Tris(pyrazolyl)borates. Syntheses and Spectroscopic and Structural Characterization of Group 1 and Group 11 Metal Complexes of [HB(3,5-(CF(3))(2)Pz)(3)](-) and [HB(3-(CF(3))Pz)(3)](-)

The fluorinated tris(pyrazolyl)borate ligands [HB(3,5-(CF(3))(2)Pz)(3)](-) and [HB(3-(CF(3))Pz)(3)](-) (where Pz = pyrazolyl) have been synthesized as their sodium salts from the corresponding pyrazoles and NaBH(4) in high yield. These sodium complexes and the related [HB(3,5-(CF(3))(2)Pz)(3)]K(DMAC) were used as ligand transfer agents in the preparation of the copper and silver complexes [HB(3,5-(CF(3))(2)Pz)(3)]Cu(DMAC), [HB(3,5-(CF(3))(2)Pz)(3)]CuPPh(3), [HB(3,5-(CF(3))(2)Pz)(3)]AgPPh(3), and [HB(3-(CF(3))Pz)(3)]AgPPh(3). Metal complexes of the fluorinated [HB(3,5-(CF(3))(2)Pz)(3)](-) ligand have highly electrophilic metal sites relative to their hydrocarbon analogs. This is evident from the formation of stable adducts with neutral oxygen donors such as H(2)O, dimethylacetamide, or thf. Furthermore, the metal compounds derived from fluorinated ligands show fairly long-range coupling between fluorines of the trifluoromethyl groups and the hydrogen, silver, or phosphorus. The solid state structures show that the fluorines are in close proximity to these nuclei, thus suggesting a possible through-space coupling mechanism. Crystal structures of the sodium adducts exhibit significant metal-fluorine interactions. The treatment of [HB(3,5-(CF(3))(2)Pz)(3)]Na(H(2)O) with Et(4)NBr led to [Et(4)N][HB(3,5-(CF(3))(2)Pz)(3)], which contains a well-separated [Et(4)N](+) cation and the [HB(3,5-(CF(3))(2)Pz)(3)](-) anion in the solid state. Crystal data with Mo Kalpha (lambda = 0.710 73 ?) at 193 K: [HB(3,5-(CF(3))(2)Pz)(3)]Na(H(2)O), C(15)H(6)BF(18)N(6)NaO, a = 7.992(2) ?, b = 15.049(2) ?, c = 9.934(2) ?, beta = 101.16(2) degrees, monoclinic, P2(1)/m, Z = 2; [{HB(3-(CF(3))Pz)(3)}Na(thf)](2), C(32)H(30)B(2)F(18)N(12)Na(2)O(2), a = 9.063(3) ?, b = 10.183(2) ?, c = 12.129(2) ?, alpha = 94.61(1) degrees, beta = 101.16(2) degrees, gamma = 95.66(2) degrees, triclinic, &Pmacr;1, Z = 1; [HB(3,5-(CF(3))(2)Pz)(3)]Cu(DMAC), C(19)H(13)BCuF(18)N(7)O, a = 15.124(4) ?, b = 8.833(2) ?, c = 21.637(6) ?, beta = 105.291(14) degrees, monoclinic, P2(1)/n, Z = 4; [HB(3,5-(CF(3))(2)Pz)(3)]CuPPh(3), C(33)H(19)BCuF(18)N(6)P, a = 9.1671(8) ?, b = 14.908(2) ?, c = 26.764(3) ?, beta = 94.891(1) degrees, monoclinic, P2(1)/c, Z = 4; [HB(3,5-(CF(3))(2)Pz)(3)]AgPPh(3).0.5C(6)H(14), C(36)H(26)AgBF(18)N(6)P, a = 13.929(2) ?, b = 16.498(2) ?, c = 18.752(2) ?, beta = 111.439(6) degrees, monoclinic, P2(1)/c, Z = 4; [Et(4)N][HB(3,5-(CF(3))(2)Pz)(3)], C(23)H(24)BF(18)N(7), a = 10.155(2) ?, b = 18.580(4) ?, c = 16.875(5) ?, beta = 99.01(2) degrees, monoclinic, P2(1)/n, Z = 4.