Dataset of polyoxometalate-assisted -heterocyclic carbene gold(I) complexes.

The present paper is the Supplemental materials for our original paper entitled "highly active, homogeneous catalysis by polyoxometalate-assisted -heterocyclic carbene gold(I) complexes for hydration of diphenylacetylene. The present article refers to the preparations of several monomeric, -heterocyclic (NHC) carbene/carboxylate (-pyrrld)/gold(I) complexes, [Au(-pyrrld)(NHC)] (NHC = IMes (), BIPr (), IF (), IBu ()), which were used for homogenous catalysis of the hydration reaction of diphenylacetylene to afford deoxybenzoin. The article also includes the preparations of the precursor complexes, [AuCl(NHC)] (NHC = IPr, IMes, BIPr, IF, IBu), and novel X-ray crystallography of the separately prepared [Au(IPr)(HO)][α-PWO]·7EtO (), summary of crystal data of (), and selected bond distances (Å) and angles (deg) of ().

Polyoxometalate-Assisted, One-Pot Synthesis of a Pentakis[(triphenylphosphane)gold]ammonium(2+) Cation Containing Regular Trigonal-Bipyramidal Geometries of Five Bonds to Nitrogen.

Novel intercluster compounds consisting of pentakis[(triphenylphosphane)gold]ammonium(2+) cation (1) and Keggin polyoxometalate (POM) anions, i.e., {[Au(PPh)](μ-N)}[α-PMO] (1-PW for M = W; 1-PMo for M = Mo), were synthesized in 30-36% yield by one-pot reaction of the protonic acid form of the Keggin POMs, H[α-PMO]·nHO (n = 13 for M = W; n = 15 for M = Mo) with monomeric (triphenylphosphane)gold(I) carboxylate [Au(RS-pyrrld)(PPh)] [RS-Hpyrrld = (RS)-2-pyrrolidone-5-carboxylic acid] in the presence of aqueous NH at a molar ratio of 2:15:x (x = 3 for 1-PW; x = 7.

Synthesis and Molecular Structure of a Novel Compound Containing a Carbonate-Bridged Hexacalcium Cluster Cation Assembled on a Trimeric Trititanium(IV)-Substituted Wells-Dawson Polyoxometalate.

A novel compound containing a hexacalcium cluster cation, one carbonate anion, and one calcium cation assembled on a trimeric trititanium(IV)-substituted Wells-Dawson polyoxometalate (POM), [{Ca(CO)(μ-OH)(OH)}(PWTiO)Ca(OH)] (CaTiTrimer), was obtained as the NaCa salt (NaCa-CaTiTrimer) by the reaction of calcium chloride with the monomeric trititanium(IV)-substituted Wells-Dawson POM species "[PWTiO(OH)]" (TiMonomer). TiMonomer was generated in situ under basic conditions from the separately prepared tetrameric species with bridging Ti(OH) groups and an encapsulated Cl ion, [{PWTiO(OH)}{μ-Ti(HO)}Cl] (TiTetramer). The NaCa salt of CaTiTrimer was characterized by complete elemental analysis, thermogravimetric (TG) and differential thermal analyses (DTA), FTIR, single-crystal X-ray structure analysis, and solution W and P NMR spectroscopy.

Crystal structure of -poly[silver(I)-μ-l-valinato-κ:].

The reaction of AgO with l-valine (l-Hval, CHNO) in a 1:2 molar ratio in water, followed by vapour diffusion, afforded a coordination polymer of the title compound, [Ag(CHNO)] , with N-Ag-O repeat units, which is classified as a type III silver(I) complex with amino acid ligands. The asymmetric unit consists of two independent units of [Ag(l-val)]. In the crystal, the polymeric chains run along [101], and neighbouring chains are linked a weak Ag⋯Ag inter-action and N-H⋯O hydrogen bonds.

Synthesis, characterization, and structure-activity relationship of the antimicrobial activities of dinuclear N-heterocyclic carbene (NHC)-silver(I) complexes.

The three dinuclear silver(I) complexes of N-heterocyclic carbene (NHC) ligands, [Ag(L-1a)](PF)·2CHCN (Ag-1a), [Ag(L-2)](PF)·HO (Ag-2), and [Ag(L-4)](PF)·2CHCN (Ag-4), were synthesized by reactions of AgO with the corresponding PF salt of the NHC precursors indicated as HL-1(PF), HL-2(PF), and HL-4(PF). HL-1(PF), which is the precursor of ligand L-1, was formed as mixed crystals of two geometric isomers, i.e.

The effect of counteranions on the molecular structures of phosphanegold(i) cluster cations formed by polyoxometalate (POM)-mediated clusterization.

The effect of counteranions on the molecular structures of phosphanegold(i) cluster cations formed by polyoxometalate (POM)-mediated clusterization was investigated. A novel intercluster compound, [{(AuLCl)2(μ-OH)}2]3[α-PMo12O40]2·3EtOH (1-PMo12), was obtained as orange-yellow plate crystals in 12.0% yield from a 6 : 1 molar ratio reaction of the monomeric phosphanegold(i) carboxylato complex [Au(RS-pyrrld)(LCl)] (RS-Hpyrrld = RS-2-pyrrolidone-5-carboxylic acid; LCl = tris(4-chlorophenyl)phosphane) in CH2Cl2 with the free acid-form of Keggin polyoxometalate (POM), H3[α-PMo12O40]·14H2O.

Synthesis and Molecular Structure of a Water-Soluble, Dimeric Tri-Titanium(IV)-Substituted Wells-Dawson Polyoxometalate Containing Two Bridging (C5Me5)Rh2+ Groups.

A novel trititanium(IV)-substituted Wells-Dawson polyoxometalate (POM)-based organometallic complex, i.e., a dimeric POM containing two bridging Cp*Rh(2+) groups (Cp* = C5Me5) or [{α-P2W15Ti3O60(OH)2}2(Cp*Rh)2](16-) (D-1) with Ci symmetry, was synthesized in an analytically pure form by a 1:2 -molar ratio reaction of the organometallic precursor [Cp*RhCl2]2 with the separately prepared, monomeric trititanium(IV)-substituted Wells-Dawson POM, "[P2W15Ti3O59(OH)3](9-)" (M-1).

Two types of tetranuclear phosphanegold(I) cations as dimers of dinuclear units, [{(Au{P(p-RPh)3})2(μ-OH)}2]2+ (R = Me, F), synthesized by polyoxometalate-mediated clusterization.

Novel intercluster compounds [{(Au{P(p-RPh)3})2(μ-OH)}2]3[α-PM12O40]2·nEtOH (R = Me, M = W for 1; R = Me, M = Mo for 2; R = F, M = Mo for 3) were synthesized by the polyoxometalate (POM)-mediated clusterization of monomeric phosphanegold(I) complexes, and unequivocally characterized by elemental analysis, TG/DTA, FTIR, X-ray crystallography, and (1)H and (31)P{(1)H} NMR. In each cluster cation, two digold(I) units, {Au{P(p-RPh)3})2(μ-OH)}(+), dimerized to form the tetragold(I) cluster cation by interdimer aurophilic interactions, i.e.

Novel intercluster compound between a heptakis{triphenylphosphinegold(I)}dioxonium cation and an α-Keggin polyoxometalate anion.

A novel intercluster compound, [{{Au(PPh(3))}(4)(μ(4)-O)}{{Au(PPh(3))}(3)(μ(3)-O)}][α-PW(12)O(40)]·EtOH (1) constructed between a heptakis{triphenylphosphinegold(i)}dioxonium cation and an α-Keggin polyoxometalate (POM) is synthesized and unequivocally characterized by elemental analysis, TG/DTA, FTIR, X-ray crystallography, solid-state CPMAS (31)P NMR and solution ((1)H, (31)P{(1)H}) NMR. The heptagold(i) cluster was formed during the course of carboxylate elimination of a monomeric phosphinegold(i) carboxylate precursor, i.e.

Syntheses, structures, and antimicrobial activities of remarkably light-stable and water-soluble silver complexes with amino acid derivatives, silver(I) N-acetylmethioninates.

Reaction of L- and DL-N-acetylmethionine (Hacmet) and Ag(2)O in water at ambient temperature afforded the remarkably light-stable silver complexes {[Ag(L-acmet)]}(n) (1) and {[Ag(2)(D-acmet)(L-acmet)]}(n) (2), respectively. The color of the solids and aqueous solutions of 1 and 2 did not change for more than 1 month under air without any shields. The light stability of these two silver(I) complexes is much higher than that of silver(I) methioninate {[Ag(2)(D-met)(L-met)]}(n) (3) (Hmet = methionine), silver(I) S-methyl-L-cysteinate {[Ag(L-mecys)]}(n) (4), and silver(I) L-cysteinate {[Ag(L-Hcys)]}(n) (5).

Synthesis and structure of dawson polyoxometalate-based, multifunctional, inorganic-organic hybrid compounds: organogermyl complexes with one terminal functional group and organosilyl analogues with two terminal functional groups.

Four novel multifunctional polyoxometalate (POM)-based inorganic-organic hybrid compounds, [α(2)-P(2)W(17)O(61){(RGe)}](7-) (Ge-1, R(1) = HOOC(CH(2))(2(-)) and Ge-2, R(2) = H(2)C═CHCH(2(-))) and [α(2)-P(2)W(17)O(61){(RSi)(2)O}](6-) (Si-1, R(1) and Si-2, R(2)), were prepared by incorporating organic chains having terminal functional groups (carboxylic acid and allyl groups) into monolacunary site of Dawson polyoxoanion [α(2)-P(2)W(17)O(61)](10-). In these POMs, new modification of the terminal functional groups was attained by introducing organogermyl and organosilyl groups. Dimethylammonium salts of the organogermyl complexes, (Me(2)NH(2))(7)[α(2)-P(2)W(17)O(61)(R(1)Ge)]·H(2)O MeN-Ge-1 and (Me(2)NH(2))(7)[α(2)-P(2)W(17)O(61)(R(2)Ge)]·4H(2)O MeN-Ge-2, were obtained as analytically pure crystals, in 22.

Encapsulation of anion/cation in the central cavity of tetrameric polyoxometalate, composed of four trititanium(IV)-substituted α-Dawson subunits, initiated by protonation/deprotonation of the bridging oxygen atoms on the intramolecular surface.

Preparation and structural characterization of a novel polyoxometalate (POM), [(P(2)W(15)Ti(3)O(60.5))(4)(NH(4))](35-) 1, i.e.

Polyoxometalate (POM)-based, multi-functional, inorganic-organic, hybrid compounds: syntheses and molecular structures of silanol- and/or siloxane bond-containing species grafted on mono- and tri-lacunary Keggin POMs.

Using 3-mercaptopropyltrimethoxysilane (HS(CH₂)₃Si(OMe)₃) as a silane-coupling agent (SCA), mono- and tri-lacunary Keggin polyoxometalate (POM)-based, multi-functional, inorganic-organic, hybrid compounds, (Et₄N)₃[α-PW₁₁O₃₉{(HS(CH₂)₃Si)₂O}] EtN-1 (the 1 : 2 complex of a POM unit and organosilyl groups), (Bu₄N)₃[A-PW₉O₃₄(HS(CH₂)₃SiOH)₃] BuN-2 (the 1 : 3 complex) and (Bu₄N)₃[A-α-PW₉O₃₄(HS(CH₂)₃SiO)₃(Si(CH₂)₃SH)] BuN-3 (the 1 : 4 complex) were synthesized and unequivocally characterized by elemental analysis, thermogravimetric and differential thermal analyses (TG/DTA), FTIR, solid-state (²⁹Si and ³¹P) CPMAS NMR, solution (²⁹Si, ³¹P, ¹H and ¹³C) NMR, and X-ray crystallography. [Note: The moieties of their polyoxoanions are abbreviated simply as 1-3, respectively.] The X-ray molecular structures of EtN-1 and BuN-3 were determined.

Intercluster compound between a tetrakis{triphenylphosphinegold(I)}oxonium cation and a keggin polyoxometalate (POM): formation during the course of carboxylate elimination of a monomeric triphenylphosphinegold(I) carboxylate in the presence of POMs.

The preparation and structural characterization of a novel intercluster compound, [{Au(PPh(3))}(4)(μ(4)-O)](3)[α-PW(12)O(40)](2)·4EtOH (1), constructed between a tetrakis{triphenylphosphinegold(I)}oxonium cation and a saturated α-Keggin polyoxometalate (POM) are described. The tetragold(I) cluster oxonium cation was formed during the course of carboxylate elimination of a monomeric phosphinegold(I) carboxylate complex, i.e.

Cyclic oligomer of oxide clusters through a siloxane bond. Synthesis and structure of reaction products of alpha2-mono-lacunary Dawson polyoxometalate with tetrachlorosilane and tetraethoxysilane.

The title compound with the formula (Me2NH2)13H5[{alpha2-P2W17O61(Si2O)}3(micro-O)3].39H2O Me2NH(2)-1 was obtained in 12.8% (0.

Synthesis and structure of dinuclear hafnium(IV) and zirconium(IV) complexes sandwiched between 2 mono-lacunary alpha-Keggin polyoxometalates.

The synthesis and characterization of two dinuclear HfIV and ZrIV complexes sandwiched between 2 mono-lacunary alpha-Keggin polyoxometalates (POMs), i.e., (Et2NH2)8[{alpha-PW11O39Hf(micro-OH)(H2O)}2].

Sandwich-type Hf(IV) and Zr(IV)complexes composed of tri-lacunary Keggin polyoxometalates: structure of [M(3)(mu-OH)(3)(A-alpha-PW(9)O(34))(2)](9-) (M = Hf and Zr).

The syntheses and structures of hafnium(iv) and zirconium(iv) complexes with Keggin tri-lacunary polyoxometalates (POM) [A-alpha-PW(9)O(34)](9-), i.e., (Et(2)NH(2))(7)H(2)[Hf(3)(micro-OH)(3)(A-alpha-PW(9)O(34))(2)].

Syntheses, molecular structures and pH-dependent monomer-dimer equilibria of Dawson alpha2-monotitanium(IV)-substituted polyoxometalates.

The preparation and structural characterization of a novel, solid Brønsted acid based on Dawson alpha2-monotitanium(IV)-substituted polyoxometalates (POMs) are described. The free-acid form of the POM, i.e.

Synthesis, reaction and structure of a highly light-stable silver(I) cluster with an Ag4S4N4 core having a tridentate 4N-morpholyl 2-acetylpyridine thiosemicarbazone ligand: use of water-soluble silver(I) carboxylates as a silver(I) source.

A novel neutral tetrameric silver(I) cluster [Ag(mtsc)](4) was obtained from reactions of a tridentate (4)N-morpholyl 2-acetylpyridine thiosemicarbazone ligand (N'-[1-(2-pyridyl)ethylidene] morpholine-4-carbothiohydrazide, Hmtsc) and silver(I) sources containing Ag-O bonds (Ag(2)O, Ag(OAc), silver(I) 2-pyrrolidone-5-carboxylate (infinity){[Ag(Hpyrrld)](2)}, silver(I) 5-oxo-2-tetrahydrofurancarboxylate (infinity){[Ag(othf)](2)}, and silver(I) complexes with camphanic acid (infinity){[Ag(ca)]} and (infinity){[Ag(ca)(Hca)]}). The cluster was characterized by elemental analysis, TG/DTA, FTIR and single-crystal X-ray analysis in the solid state. The solution properties of the complexes were investigated using solution molecular weight measurement, ESI-MS and solution ((1)H, (13)C and (31)P) NMR spectroscopy.

Syntheses and X-ray crystal structures of zirconium(IV) and hafnium(IV) complexes containing monovacant wells-Dawson and Keggin polyoxotungstates.

The syntheses and crystal structures of a series of zirconium(IV) and hafnium(IV) complexes with Dawson monovacant phosphotungstate [alpha2-P2W17O61](10-) and in situ-generated Keggin monovacant phosphotungstate [alpha-PW11O39](7-), which was obtained by a reaction of [alpha-PW12O40](3-) with Na2CO3, are described. K15H[Zr(alpha2-P2W17O61)2].25H2O (K-1), K16[Hf(alpha2-P2W17O61)2].

Novel Ti-O-Ti bonding species constructed in a metal-oxide cluster: reaction products of bis(oxalato)oxotitanate(IV) with the dimeric, 1,2-dititanium(IV)-substituted Keggin polyoxotungstate.

The preparation and structural characterization of a novel Ti-O-Ti bonding complex constructed in a dilacunary alpha-Keggin polyoxometalate (POM), [[{Ti(ox)(H2O)}4(mu-O)3](alpha-PW10O37)](7-) (H2ox = oxalic acid) (1a), are described. The water-soluble, crystalline complex with a formula of K6H[1a].0.

Novel Ti-O-Ti bonding species constructed in a metal-oxide cluster.

The preparation and structural characterization of a novel Ti-O-Ti bonding complex constructed in the mono-lacunary alpha-Keggin polyoxometalate (POM), are described. The water-soluble, crystalline complex with a formula of K5H2[[{Ti(OH)(ox)}2(micro-O)](alpha-PW11O39)] x 13H2O 1 was prepared in 30.2% (0.

Syntheses, structures and antimicrobial activities of water-soluble silver(I)-oxygen bonding complexes with chiral and racemic camphanic acid (Hca) ligands.

Water-soluble, relatively light-stable, chiral and achiral silver(I) complexes [[Ag(2)(ca)(2)]](n) and [[Ag(2)(ca)(2)(Hca)(2)]](n)(R- and S-Hca =(1R,4S)- and (1S,4R)-4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-carboxylic acid, respectively) prepared from the reaction of Ag(2)O with chiral and racemic Hca in 1:2 and 1:4 molar ratios were characterized by elemental analysis, TG/DTA, FTIR, and solution ((1)H, (13)C and (109)Ag) and solid-state ((13)C) NMR spectroscopy.