Synthesis, structure and luminescence studies of heterometallic gold(I)-copper(I) and -silver(I) alkynyl clusters/aggregates.

A series of pentanuclear gold(I)-copper(I) and -silver(I) mixed-metal alkynyl complexes, [(n)Bu(4)N][Au(3)M(2)(C triple bond CC(6)H(4)R-p)(6)] [M = Cu, R = OMe, O(n)Bu, O(n)Hex, Me, Et; M = Ag, R = Et, O(n)Hex] have been synthesized. The complexes were found to be emissive both in the solid state and in fluid solutions. DFT calculations at the B3LYP level of theory were performed on [Au(3)M(2)(C triple bond CC(6)H(4)Me-p)(6)](-) (M = Cu, Ag) to provide an understanding on the electronic structure of the complexes.

Synthesis, photophysics, electrochemistry, theoretical, and transient absorption studies of luminescent copper(I) and silver(I) diynyl complexes. X-ray crystal structures of [Cu3(micro-dppm)3(micro3-eta1-C triple bond CC triple bond CPh)2]PF6 and [Cu3(micro-dppm)3(micro3-eta1-C triple bond CC triple bond CH)2]PF6.

A series of soluble trinuclear copper(I) and silver(I) complexes containing bicapped diynyl ligands, [M(3)(micro-dppm)(3)(micro(3)-eta(1)-C triple bond CC triple bond CR)(2)]PF(6) (M = Cu, R = Ph, C(6)H(4)-CH(3)-p, C(6)H(4)-OCH(3)-p, (n)C(6)H(13), H; M = Ag, R = Ph, C(6)H(4)-OCH(3)-p), has been synthesized and their electronic, photophysical, and electrochemical properties studied. The X-ray crystal structures of [Cu(3)(micro-dppm)(3)(micro(3)-eta(1)-C triple bond CC triple bond CPh)(2)]PF(6) and [Cu(3)(micro-dppm)(3)(micro(3)-eta(1)-C triple bond CC triple bond CH)(2)]PF(6) have been determined.

3[(dx2-y2,dxy)(pz)] excited state of binuclear copper(I) phosphine complexes: effect of copper-ligand and copper-copper interactions on excited state properties and photocatalytic reductions of the 4,4'-dimethyl-2,2'-bipyridinium ion in alcohols.

A comprehensive study of the structural and spectroscopic properties of two-, three-, and four-coordinate copper(I) complexes with aliphatic phosphine ligands is presented. All complexes described in this work are characterized by X-ray crystallography. The intramolecular Cu.

Organic triplet emissions of arylacetylide moieties harnessed through coordination to [Au(PCy(3))]+. Effect of molecular structure upon photoluminescent properties.

A family of mono- and binuclear Cy(3)P-supported gold(I) complexes containing various pi-conjugated linear arylacetylide ligands, including the two homologous series (Cy(3)P)Au(Ctbd1;CC(6)H(4))(n)()(-)(1)(Ctbd1;CPh) and (Cy(3)P)Au(Ctbd1;CC(6)H(4))(n)()Ctbd1;CAu(PCy(3)) (n = 1-4), have been prepared. X-ray crystal analyses revealed no intermolecular aurophilic interactions in their crystal lattice. The lowest-energy singlet transitions are predominately intraligand in nature and exhibit both phenyl and acetylenic (1)(pipi) character.

Syntheses, electronic absorption, emission, and ion-binding studies of platinum(III) C empty set N empty set C and terpyridyl complexes containing crown ether pendants.

A series of platinum (II) C empty set N empty set C complexes, [Pt(C empty set N empty set C) (L)] (HC empty set N empty set CH=2,6-diphenylpyridine (dppy); L=Ph(2)PB15C5 (1, B15C5=benzo[15]crown-5), Ph(2)PDMP (2, DMP=3,4-dimethoxyphenyl), pyCOA15C5 (3, A15C5=aza[15]crown-5), pyCON(CH(2)CH(2)OCH(3))(2) (4), pyC[triple bond]CB15C5 (5), pyC[triple bond]CDMP (6)) and terpyridyl complexes, [Pt(trpy)(L)](X)(2) (trpy=2,2':6',2''-terpyridine; L=Ph(2)PB15C5, X=OTf (7 a), PF(6) (7 b); X=PF(6), L=Ph(2)PDMP (8), pyC[triple bond]CB15C5 (9), and pyC[triple bond]CDMP (10)) have been successfully synthesized and characterized. The structures of 1, 3, and 7 a have been determined by X-ray crystallography. Excitation of complexes 1-6 in EtOH/MeOH (4:1 v/v) glass gave high-energy structured emission bands, assigned as derived from states of metal-perturbed intraligand (IL) origin.

Luminescent homo- and heteropolynuclear platinum(II) chalcogenido aggregates based on [Pt2E2(P empty set N)4] units (E=S, Se).

A series of homodinuclear platinum(II) complexes containing bridging chalcogenido ligands, [Pt(2)(mu-E)(2)(P empty set N)(4)] (P empty set N=dppy, E=S (1), Se (2); P empty set N=tBu-dppy, E=S (3)) (dppy=2-(diphenylphosphino)pyridine, tBu-dppy=4-tert-butyl-2-(diphenylphosphino)pyridine) have been synthesized and characterized. The nucleophilicity of the [Pt(2)E(2)] unit towards a number of d(10) metal ions and complexes has been demonstrated through the successful isolation of a number of novel heteropolynuclear platinum(II)-copper(I), -silver(I), and -gold(I) complexes: [[Pt(2)(mu(3)-E)(2)(dppy)(4)](2)Ag(3)](PF(6))(3) (E=S (4); Se (5)) and [Pt(2)(dppy)(4)(mu(3)-E)(2)M(2)(dppm)]X(2) (E=S, M=Ag, X=BF(4) (6); E=S, M=Cu, X=PF(6) (7); E=S, M=Au, X=PF(6) (8); E=Se, M=Ag, X=PF(6) (9); E=Se, M=Au, X=PF(6) (10)). Some of them display short metal.

Novel intramolecular cyclopropanation reaction of unsaturated beta-keto esters.

[reaction: see text] Fused cyclopropane beta-keto esters are versatile intermediates for the synthesis of many biologically active natural products. Here we report a new intramolecular cyclopropanation reaction of unsaturated beta-keto esters. In the presence of I(2), Et(3)N, and Lewis acids such as Mg(ClO(4))(2) and Yb(OTf)(3), beta-keto esters 1 bearing various olefin substituents were transformed to fused cyclopropanes 2 in a highly stereospecific manner with moderate to good yields.

Metal-metal interactions in dinuclear d(8) metal cyanide complexes supported by phosphine ligands. Spectroscopic properties and ab initio calculations of [M(2)(mu-diphosphine)(2)(CN)(4)] and trans-[M(phosphine)(2)(CN)(2)] (M = Pt, Ni).

Structural, spectroscopic properties on the dinuclear [M(2)(dcpm)(2)(CN)(4)] (M = Pt, 1a; Ni, 2a, dcpm = bis(dicyclohexylphosphino)methane) and [M(2)(dmpm)(2)(CN)(4)] (M = Pt, 1b; Ni, 2b, dmpm = bis(dimethylphosphino)methane) and the mononuclear trans-[M(PCy(3))(2)(CN)(2)] (M = Pt, 3; Ni, 4, PCy(3) = tricyclohexylphosphine) and theoretical investigations on the corresponding model compounds are described. X-ray structural analyses reveal Pt.Pt and Ni.

Synthesis, characterization, photophysical properties, and biological labeling studies of a series of luminescent rhenium(I) polypyridine maleimide complexes.

We report the synthesis, characterization, and photophysical properties of a series of rhenium(I) polypyridine maleimide complexes [Re(N-N)(CO)(3)(py-3-mal)](CF(3)SO(3)) [N-N = 1,10-phenanthroline, phen (1), 2,9-dimethyl-1,10-phenanthroline, 2,9-Me(2)-phen (2), 3,4,7,8-tetramethyl-1,10-phenanthroline, 3,4,7,8-Me(4)-phen (3), 4,7-diphenyl-1,10-phenanthroline, 4,7-Ph(2)-phen (4), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 2,9-Me(2)-4,7-Ph(2)-phen (5), 2,2'-biquinonine, biq (6); py-3-mal = N-(3-pyridyl)maleimide]. The X-ray crystal structure of complex 2 has been investigated. Upon excitation, the complexes exhibit intense and long-lived photoluminescence in fluid solutions at 298 K.

Synthesis, Spectroscopic Properties, and Reactivities of Bis(tosylimido)osmium(VI) Porphyrin Complexes. X-ray Crystal Structure of [Os(VI)(TPP)(NSO(2)C(6)H(4)-pCH(3))(2)] (TPP = Tetraphenylporphyrinato).

The bis(tosylimido)osmium(VI) porphyrins [Os(VI)(Por)(NTs)(2)] [Por = tetraphenylporphyrinato (TPP), meso-tetrakis(p-tolyl)porphyrinato (TTP), meso-tetrakis(4-chlorophenyl)porphyrinato (4-Cl-TPP), meso-tetrakis(4-methoxyphenyl)porphyrinato (4-MeO-TPP); Ts = tosyl] were prepared from the reactions of [Os(II)(Por)(CO)(MeOH)] with excess PhI=NTs in dichloromethane. The X-ray crystal structure of [Os(VI)(TPP)(NTs)(2)] has been determined. Crystal data for [Os(VI)(TPP)(NTs)(2)]: triclinic, space group P&onemacr; (No.

Synthesis of Bis(aliphatic amine)osmium(II), Bis(arylamido)osmium(IV), and Bis(imido)- and Oxo(imido)osmium(VI) Porphyrins.

The syntheses, characterization, and reactivity of a series of osmium porphyrins, Os(II)(Por)(H(2)NR)(2) [Por = dianions of octaethylporphyrinato (OEP), tetraphenylporphyrinato (TPP), meso-tetrakis(p-tolyl)porphyrinato (TTP), meso-tetrakis(4-chlorophenyl)porphyrinato (4-Cl-TPP), meso-tetrakis(3,4,5-trimethoxyphenyl)porphyrinato (3,4,5-MeO-TPP), R = (t)Bu; Por = TPP, R = (i)Pr], Os(II)(Por)(HNEt(2))(2) (Por = TPP, 3,4,5-MeO-TPP), Os(IV)(Por)(NHAr)(2) (Por = OEP, TPP, 3,4,5-MeO-TPP; Ar = Ph, 4-F-Ph), Os(VI)(Por)(N(t)Bu)(2) (Por = TPP, TTP, 4-Cl-TPP, 3,4,5-MeO-TPP), Os(VI)O(Por)(N(t)Bu) (Por = TPP, TTP, 4-Cl-TPP, 3,4,5-MeO-TPP), and Os(VI)O(Por)(4-F-PhN) (Por = TPP, 3,4,5-MeO-TPP) are described. The complexes Os(Por)(HNAr)(2) are prepared from the reactions of Os(Por)(N(2))(THF) with arylamines in aerobic tetrahydrofuran. Air oxidations of Os(Por)(H(2)N(t)Bu)(2) in tetrahydrofuran and in the presence of H(2)N(t)Bu give OsO(Por)(N(t)Bu) and Os(Por)(N(t)Bu)(2).