Aurophilic interactions in cationic gold complexes with two isocyanide ligands. Polymorphic yellow and colorless forms of [(cyclohexyl isocyanide)2AuI](PF6) with distinct luminescence

Crystallographic studies of yellow and colorless forms of [(C(6)H(11)NC)(2)Au(I)](PF(6)) show that they are polymorphs with differing, but close, contacts between the gold atoms which form extended chains. In the colorless polymorph the gold cations form linear chains with a short Au...Au contact (3.1822(3) A) indicative of an aurophilic attraction. The structure of the yellow polymorph is more complicated with four independent cations forming kinked, slightly helical chains with very short Au...Au contacts of 2.9803(6), 2.9790(6), 2.9651(6), and 2.9643(6) A. However, in the related compound, [(CH(3)NC)(2)Au(I)](PF(6)), each cation is surrounded by six hexafluorophosphate ions and there is no close Au...Au contact despite the fact that the isocyanide ligand has less steric bulk. The crystalline colorless and yellow polymorphs are both luminescent at 298 K, lambda(max): 424 nm (colorless) or 480 nm (yellow). Colorless solutions of the two polymorphs have identical absorption spectra and are nonluminescent at room temperature. Freezing solutions of [(C(6)H(11)NC)(2)Au(I)](PF(6)) produces intense luminescence which varies depending upon the solvent involved. Each polymorph melts to give a colorless but luminescent liquid which reverts to the yellow polymorph upon cooling.     

Remarkable variations in the luminescence of frozen solutions of [Au[C(NHMe)(2)](2)](PF(6)) x 0.5(acetone). Structural and spectroscopic studies of the effects of anions and solvents on Gold(I) carbene complexes

The unusual luminescence behavior of the two-coordinate gold(I) carbene complex, [Au[C(NHMe)(2)](2)](PF(6)) x 0.5(acetone), is reported. Upon freezing in a liquid N(2) bath, the colorless, nonluminescent solutions of [Au[C(NHMe)(2)](2)](PF(6)) x 0.5(acetone) become intensely luminescent. Strikingly, the colors of the emission differ in different solvents and appear only after the solvent has frozen. Solid [Au[C(NHMe)(2)](2)](PF(6)) x 0.5(acetone) is also luminescent, and the luminescence is attributed to the formation of extended chains of gold(I) centers that are connected through aurophilic attractions. Crystallographic studies of [Au[C(NHMe)(2)](2)](PF(6)) x 0.5(acetone) and [Au[C(NHMe)(2)](2)](BF(4)), which is also luminescent, reveal that both involve extended chains of cations and that the anions are hydrogen bonded to the cations through cation N-H groups. However, these chains differ in the Au...Au separations in each and in the carbene ligand orientations. In contrast, [Au[C(NMe(2))(NHMe)](2)](PF(6)) forms a colorless, nonluminescent solid, and in that solid there are no Au...Au interactions, a factor which supports the contention that aggregated species are responsible for the luminescence of [Au[C(NHMe)(2)](2)](PF(6)) x 0.5(acetone) in the solid state and in frozen solutions.     

Seeing luminescence appear as crystals crumble. Isolation and subsequent self-association of individual [(C6H11NC)2Au]+ ions in crystals

Non-luminescent, isostructural crystals of [(C₆H₁₁NC)₂Au](EF₆)·C₆H₆ (E = As, Sb) lose benzene upon standing in air to produce green luminescent (E = As) or blue luminescent (E = Sb) powders. Previous studies have shown that the two-coordinate cation, [(C₆H₁₁NC)₂Au]⁺, self-associates to form luminescent crystals that contain linear or nearly linear chains of cations and display unusual polymorphic, vapochromic, and/or thermochromic properties. Here, we report the formation of non-luminescent crystalline salts in which individual [(C₆H₁₁NC)₂Au]⁺ ions are isolated from one another. In [(C₆H₁₁NC)₂Au](BArF₂₄) ((BArF₂₄)⁻ is tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) each cation is surrounded by two anions that prohibit any close approach of the gold ions. Crystallization of [(C₆H₁₁NC)₂Au](EF₆) (E = As or Sb, but not P) from benzene solution produces colorless, non-emissive crystals of the solvates [(C₆H₁₁NC)₂Au](EF₆)·C₆H₆. These two solvates are isostructural and contain columns in which cations and benzene molecules alternate. With the benzene molecules separating the cations, the shortest distances between gold ions are 6.936(2) Å for E = As and 6.9717(19) Å for E = Sb. Upon removal from the mother liquor, these crystals crack due to the loss of benzene from the crystal and form luminescent powders. Crystals of [(C₆H₁₁NC)₂Au](SbF₆)·C₆H₆ that powder out form a pale yellow powder with a blue luminescence with emission spectra and powder X-ray diffraction data that show that the previously characterized [(C₆H₁₁NC)₂Au](SbF₆) is formed. In the process, the distances between the gold(i) ions decrease to ∼3 Å and half of the cyclohexyl groups move from an axial orientation to an equatorial one. Remarkably, when crystals of [(C₆H₁₁NC)₂Au](AsF₆)·C₆H₆ stand in air, they lose benzene and are converted into the yellow, green-luminescent polymorph of [(C₆H₁₁NC)₂Au](AsF₆) rather than the colorless, blue-luminescent polymorph. Paradoxically, the yellow, green-luminescent powder that forms as well as authentic crystals of the yellow, green-luminescent polymorph of [(C₆H₁₁NC)₂Au](AsF₆) are sensitive to benzene vapor and are converted by exposure to benzene vapor into the colorless, blue-luminescent polymorph.

Non-luminescent crystals of [(C₆H₁₁NC)₂Au](AsF₆)·C₆H₆ readily lose benzene to form the green-luminescent polymorph of [(C₆H₁₁NC)₂Au](AsF₆) rather than the blue-luminescent polymorph.     

Colorless, non-luminescent; colorless, luminescent; and yellow, luminescent crystals of the cation [Au{C(NHCH(3))(NHCH(2)CH(2)OH)}(2)](+). The roles of anions and hydrogen bonding in determining the aggregation of two-coordinate gold(I) cations

Crystallographic and luminescence studies on salts of the two-coordinate carbene cation, [Au{C(NHCH(3))(NHCH(2)CH(2)OH)}(2)](+), demonstrate the ability of the cation to exist in three different states of aggregation. In colorless, non-luminescent [Au{C(NHCH(3))(NHCH(2)CH(2)OH)}(2)]Cl the cation crystallizes as a monomer with the nearest gold(i) center 6.7890(11) A away. Colorless, luminescent [Au{C(NHCH(3))(NHCH(2)CH(2)OH)}(2)]AsF(6) forms dimers with an AuAu separation of 3.1288(4) A. These dimers form weakly associated extended chains of cations with additional AuAu separations of 3.6625(5) A. [Au{C(NHCH(3))(NHCH(2)CH(2)OH)}(2)]PF(6) is isostructural. Yellow, luminescent [Au{C(NHCH(3))(NHCH(2)CH(2)OH)}(2)](3)(AsF(6))(2)Cl.0.5(H(2)O)(2) and [Au{C(NHCH(3))(NHCH(2)CH(2)OH)}(2)](3)(PF(6))(2)Cl.0.5(H(2)O)(2) form trimers that further aggregate into extended chains with rather short AuAu separations of 3.1301(14) A, 3.1569(14) A and 3.1415(14) A. Absorption, emission and excitation spectra are reported for these salts. The excitation and emission results from the interactions between the gold centers and involves transitions between the filled d(z)((2)) band and the empty p(z) bands with the z axis pointing along the chain of cations.     

Adventures in crystallization. Crystalline salts containing one, two, or even three chemically distinct cations obtained from solutions of [(cyclohexyl isocyanide)(4)Rh(I)]+

By judicious selection of crystallization conditions, it has been possible to obtain the salts of a common building block, [(RNC)4Rh(I)]+, in single-crystal form suitable for X-ray diffraction. Salts that contain a single type of cation include deep green [(C6H11NC)12Rh(I)3](SbF6)3, deep green [(C6H11NC)12Rh(I)3](AsF6)3, and straw yellow [(C6H11NC)8Rh(II)2Cl2](BF4)2 (in addition to the previously isolated trimeric deep green [(i-PrNC)12RhI3]Cl3 x 4.5 H2O, monomeric, [(C6H11NC)4 Rh(I)](BPh4), and [(i-PrNC)4Rh(I)](BPh4) (both yellow), and red, dimeric [(C6H11NC)8Rh(I)2]Cl2 x 0.5C6H6 x 2H2O). Ordered crystals of [(C6H11NC)12Rh(I)3](SbF6)3 contain linear Rh3 units, while those of [(C6H11NC)12Rh(I)3](AsF6)3 show disorder which is consistent with the presence of linear or bent Rh3 units. The formation of green [(C6H11NC)12Rh(V/III)3Cl2][(C6H11NC)12Rh(I)3]Cl6, and brown [(C6H11NC)12Rh(V/III)3Cl2][(C6H11NC)8Rh(I)2][(C6H11NC)4RhI]Cl6 x 16H2O x 3C6H6 along with unidentified red-brown cubes from an air-exposed solution of [(C6H11NC)4Rh(I)]Cl is reported. As their formulas indicate, green [(C6H11NC)12Rh(V/III)3Cl2][(C6H11NC)12Rh(I)3]Cl6, and brown [(C6H11NC)12Rh(V/III)3Cl2][(C6H11NC)8Rh(I)2][(C6H11NC)8Rh(I)]Cl6 x 16H2O x 3C6H6 contain two or three chemically distinct cations, respectively, but again are built from a common precursor, [(C6H11NC)4Rh(I)]+.     

Reactions of a gold(I) thiolate complex [Au(Tab)(2)](2)(PF(6))(2) (Tab = 4-(trimethylammonio)benzenethiolate) with diphosphine ligands

Reactions of a gold(i) thiolate complex [Au(Tab)(2)](2)(PF(6))(2) (Tab = 4-(trimethylammonio)benzenethiolate) with equimolar 1,2-bis(diphenylphosphine)ethane (dppe), 1,3-bis-(diphenylphosphine)propane (dppp) or 1,4-bis-(diphenylphosphine)butane (dppb) in MeOH-DMF-CH(2)Cl(2) gave rise to three polymeric complexes [Au(2)(Tab)(2)(dppe)](2)(PF(6))(4)·2MeOH (1·2MeOH), [Au(2)(Tab)(2)(dppp)]Cl(2)·0.5MeOH·4H(2)O (2·0.5MeOH·4H(2)O), and [Au(4)(μ-Tab)(2)(Tab)(2)(dppb)](PF(6))(4)·4DMF (3·4DMF), respectively. Analogous reaction of 1 with dppb in DMF/C(2)H(4)Cl(2) produced one tetranuclear complex [Au(2)(μ-Tab)(Tab)(2)](2)Cl(4)·2DMF·4H(2)O (4·2DMF·4H(2)O). Complexes 1-4 were characterized by elemental analysis, IR spectra, UV-vis spectra, (1)H and (31)P{(1)H} NMR and single crystal X-ray analysis. Compounds 1 and 2 consist of [Au(Tab)](2) dimeric fragments that are bridged by dppe or dppp ligands to form a 1D linear chain extending along the a axis. For 3, each [Au(4)(Tab)(2)(μ-Tab)(2)] fragment is linked by a pair of dppb ligands to afford another 1D chain extending along the c axis. For 4, the four [Au(Tab)](+) fragments are linked by two Au-Au bonds and two doubly bridging Tab ligands to form a {[Au(Tab)](4)(μ-Tab)(2)} chair-like cyclohexane structure. Hydrogen-bonding interactions in 2 and 4 lead to the formation of interesting 2D hydrogen-bonded networks. The luminescent properties of 1-4 in solid state were also investigated.     

Metal(II) hexafluorophosphates(V) (M = Sr, Pb) containing XeF(2)-coordinated metal ions [M(XeF(2))(3)](PF(6))(2), [Pb(3)(XeF(2))(11)](PF(6))(6), and [Sr(3)(XeF(2))(10)](PF(6))(6)

From the system MF(2)/PF(5)/XeF(2)/anhydrous hydrogen fluoride (aHF), four compounds [Sr(XeF(2))(3)](PF(6))(2), [Pb(XeF(2))(3)](PF(6))(2), [Sr(3)(XeF(2))(10)](PF(6))(6), and [Pb(3)(XeF(2))(11)](PF(6))(6) were isolated and characterized by Raman spectroscopy and X-ray single-crystal diffraction. The [M(XeF(2))(3)](PF(6))(2) (M = Sr, Pb) compounds are isostructural with the previously reported [Sr(XeF(2))(3)](AsF(6))(2). The structure of [Sr(3)(XeF(2))(10)](PF(6))(6) (space group C2/c; a = 11.778(6) Angstrom, b = 12.497(6) Angstrom, c = 34.60(2) Angstrom, beta = 95.574(4) degrees, V = 5069(4) Angstrom(3), Z = 4) contains two crystallographically independent metal centers with a coordination number of 10 and rather unusual coordination spheres in the shape of tetracapped trigonal prisms. The bridging XeF(2) molecules and one bridging PF(6)- anion, which connect the metal centers, form complicated 3D structures. The structure of [Pb(3)(XeF(2))(11)](PF(6))(6) (space group C2/m; a = 13.01(3) Angstrom, b = 11.437(4) Angstrom, c = 18.487(7) Angstrom, beta = 104.374(9) degrees, V = 2665(6) Angstrom(3), Z = 2) consists of a 3D network of the general formula {[Pb(3)(XeF(2))(10)](PF(6))(6)}n and a noncoordinated XeF(2) molecule fixed in the crystal structure only by weak electrostatic interactions. This structure also contains two crystallographically independent Pb atoms. One of them possesses a unique homoleptic environment built up by eight F atoms from eight XeF(2) molecules in the shape of a cube, whereas the second Pb atom with a coordination number of 9 adopts the shape of a tricapped trigonal prism common for lead compounds. [Pb(3)(XeF(2))(11)](PF(6))(6) and [Sr(3)(XeF(2))(10)](PF(6))(6) are formed when an excess of XeF(2) is used during the process of the crystallization of [M(XeF(2))(3)](PF(6))(2) from their aHF solutions.     

X-ray Crystallographic Study of the Ruthenium Blue Complexes [Ru(2)Cl(3)(tacn)(2)](PF(6))(2).4H(2)O, [Ru(2)Br(3)(tacn)(2)](PF(6))(2).2H(2)O, and [Ru(2)I(3)(tacn)(2)](PF(6))(2): Steric Interactions and the Ru-Ru "Bond Length"

X-ray crystal structures are reported for the following complexes: [Ru(2)Cl(3)(tacn)(2)](PF(6))(2).4H(2)O (tacn = 1,4,7-triazacyclononane), monoclinic P2(1)/n, Z = 4, a = 14.418(8) ?, b = 11.577(3) ?, c = 18.471(1) ?, beta = 91.08(5) degrees, V = 3082 ?(3), R(R(w)) = 0.039 (0.043) using 4067 unique data with I > 2.5sigma(I) at 293 K; [Ru(2)Br(3)(tacn)(2)](PF(6))(2).2H(2)O, monoclinic P2(1)/a, Z = 4, a = 13.638(4) ?, b = 12.283(4) ?, c = 18.679(6) ?, beta = 109.19(2) degrees, V = 3069.5 ?(3), R(R(w)) = 0.052 (0.054) using 3668 unique data with I > 2.5sigma(I) at 293 K; [Ru(2)I(3)(tacn)(2)](PF(6))(2), cubic P2(1)/3, Z = 3, a = 14.03(4) ?, beta = 90.0 degrees, V = 2763.1(1) ?(3), R (R(w)) = 0.022 (0.025) using 896 unique data with I > 2.5sigma(I) at 293 K. All of the cations have cofacial bioctahedral geometries, although [Ru(2)Cl(3)(tacn)(2)](PF(6))(2).4H(2)O, [Ru(2)Br(3)(tacn)(2)](PF(6))(2).2H(2)O, and [Ru(2)I(3)(tacn)(2)](PF(6))(2) are not isomorphous. Average bond lengths and angles for the cofacial bioctahedral cores, [N(3)Ru(&mgr;-X)(3)RuN(3)](2+), are compared to those for the analogous ammine complexes [Ru(2)Cl(3)(NH(3))(6)](BPh(4))(2) and [Ru(2)Br(3)(NH(3))(6)](ZnBr(4)). The Ru-Ru distances in the tacn complexes are longer than those in the equivalent ammine complexes, probably as a result of steric interactions.     

New structural features of unsupported chains of metal ions in luminescent [(NH3)4Pt][Au(CN)2]2 x 1.5(H2O) and related salts

Luminescent [(NH(3))(4)Pt][Au(CN)(2)](2).1.5(H(2)O), which forms from aqueous solutions of [(NH(3))(4)Pt]Cl(2) and K[Au(CN)(2)], crystallizes with extended chains of the two ions with multiple close Pt...Au (3.2804(4) and 3.2794(4) A) and Au...Au (3.2902(5), 3.3312(5), and 3.1902(4) A) contacts. Nonluminescent [(NH(3))(4)Pt][Ag(CN)(2)](2).1.4(H(2)O) is isostructural with [(NH(3))(4)Pt][Au(CN)(2)](2).1.5(H(2)O). Treatment of [(NH(3))(6)Ni]Cl(2) with K[Au(CN)(2)] forms [(NH(3))(2)Ni][Au(CN)(2)](2) in which the [Au(CN)(2)](-) ions function as nitrile ligands toward nickel, which assumes a six-coordinate structure with trans NH(3) ligands. The [Au(CN)(2)](-) ions self-associate into linear columns with close Au...Au contacts of 3.0830(5) A, and pairs of gold ions in these chains make additional but longer (3.4246(5) A) contacts with other gold ions.     

Structural distortions upon oxidation in heteroleptic [Cp(2)W(dmit)] tungsten dithiolene complex: combined structural, spectroscopic, and magnetic studies

Four different cation radical salts are obtained upon electrocrystallization of [Cp(2)W(dmit)] (dmit = 1,3-dithiole-2-thione-4,5-dithiolato) in the presence of the BF(4)(-), PF(6)(-), Br(-), and [Au(CN)(2)](-) anions. In these formally d(1) cations, the WS(2)C(2) metallacycle is folded along the S···S hinge to different extents in the four salts, an illustration of the noninnocent character of the dithiolate ligand. Structural characteristics and the charge distribution on atoms, for neutral and ionized complexes with various folding angles, were calculated using DFT methods, together with the normal vibrational modes and theoretical Raman spectra. Raman spectra of neutral complex [Cp(2)W(dmit)] and its salts formed with BF(4)(-), AsF(6)(-), PF(6)(-), Br(-), and [Au(CN)(2)](-) anions were measured using the red excitation (λ = 632.8 nm). A correlation between the folding angle of the metallacycle and the Raman spectroscopic properties is analyzed. The bands attributed to the C═C and C-S stretching modes shift toward higher and lower frequencies by about 0.3-0.4 cm(-1) deg(-1), respectively. The solid state structural and magnetic properties of the three salts are analyzed and compared with those of the corresponding molybdenum complexes. Temperature dependence of the magnetic susceptibility shows the presence of one-dimensional antiferromagnetic interactions in the BF(4)(-), PF(6)(-), and [Au(CN)(2)](-) salts, while an antiferromagnetic ground state is identified in the Br(-) salt below T(Ne?el) = 7 K. Interactions are systematically weaker in the tungsten salts than in the isostructural molybdenum analogs, a consequence of the decreased spin density on the dithiolene ligand in the tungsten complexes.     

Variation in crystallization conditions allows the isolation of trimeric as well as dimeric and monomeric forms of [(alkyl isocyanide)4RhI]+

Trimeric green [(i-PrNC)12Rh(I)3]Cl3.4.5H2O, monomeric [(C6H11NC)4Rh(I)](BPh4) and [(i-PrNC)4Rh(I)](BPh4) (both yellow), and red, dimeric [(C6H11NC)8Rh(I)2]Cl2.0.5C6H6.2H2O have been crystallized.     

Gold(I) complexes bearing mixed-donor ligands derived from N-heterocyclic carbenes

The new 2-phenylthiocarbamoyl-1,3-dimesitylimidazolium inner salt (IMes·CSNPh) reacts with [AuCl(L)] in the presence of NH(4)PF(6) to yield [(L)Au(SCNPh·IMes)](+) (L = PMe(3), PPh(3), PCy(3), CNBu(t)). The carbene-containing precursor [(IDip)AuCl] reacts with IMes·CSNPh under the same conditions to afford the complex [(IDip)Au(SCNPh·IMes)](+) (IDip = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene). Treatment of the diphosphine complex [(dppm)(AuCl)(2)] with one equivalent of IMes·CSNPh yields the digold metallacycle, [(dppm)Au(2)(SCNPh·IMes)](2+), while reaction of [L(2)(AuCl)(2)] with two equivalents of IMes·CSNPh results in [(L(2)){Au(SCNPh·IMes)}(2)](2+) (L(2) = dppb, dppf, or dppa; dppb = 1,4-bis(diphenylphosphino)butane, dppf = 1,1'-bis(diphenylphosphino)ferrocene, dppa = 1,4-bis(diphenylphosphino)acetylene). The homoleptic complex [Au(SCNPh·IMes)(2)](+) is formed on reaction of [AuCl(tht)] (tht = tetrahydrothiophene) with two equivalents of the imidazolium-2-phenylthiocarbamoyl ligand. This product reacts with AgOTf to yield the mixed metal compound [AuAg(SCNPh·IMes)(2)](2+). Over time, the unusual trimetallic complex [Au(AgOTf)(2)(SCNPh·IMes)(2)](+) is formed. The sulfur-oxygen mixed-donor ligands IMes·COS and SIMes·COS (SIMes = 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) were used to prepare [(L)Au(SOC·IMes)](+) and [(L)Au(SOC·SIMes)](+) from [(L)AuCl] (L = PPh(3), CN(t)Bu). The bimetallic examples [(dppf){Au(SOC·IMes)}(2)](2+) and [(dppf){Au(SOC·SIMes)}(2)](2+) were synthesized from the reaction of [(dppf)(AuCl)(2)] with the appropriate ligand. Reaction of [(tht)AuCl] with one equivalent of IMes·COS or SIMes·COS yields [Au(SOC·IMes)(2)](+) and [Au(SOC·SIMes)(2)](+), respectively. The compounds [(Ph(3)P)Au(SCNPh·IMes)]PF(6), [(Cy(3)P)Au(SCNPh·IMes)]PF(6) and [Au(AgOTf)(2)(SCNPh·IMes)(2)]OTf were characterized crystallographically.     

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.     

Synthesis and properties of gold alkene complexes. Crystal structure of [Au(bipy(oXyl))(eta(2)-CH(2)=CHPh)](PF(6)) and DFT calculations on the model cation [Au(bipy)(eta(2)-CH(2)=CH(2))](+)

Unprecedented 16-electron gold(i) olefin complexes of general formula [Au(bipy(R,R'))(eta(2)-olefin)](PF(6)) and [Au(2)(bipy(R,R'))(2)(mu-eta(2):eta(2)-diolefin)](PF(6))(2) (bipy(R,R') = 6-substituted-2,2'-bipyridine) have been prepared by reaction of dinuclear gold(III) oxo complexes [Au(2)(bipy(R,R'))(2)(mu-O)(2)](PF(6))(2) with the appropriate olefin. The X-ray crystal structures of two mononuclear complexes (olefin = styrene) show in-plane coordination of the olefin and a C[double bond, length as m-dash]C bond distance considerably lengthened with respect to the free olefin. The spectroscopic properties of the complexes are discussed and compared with those of analogous d(10) metal derivatives. Both structural and spectroscopic information indicate a substantial contribution of pi-back-donation to the Au-olefin bond in the three-coordinate species. Theoretical calculations carried out at the hybrid-DFT level on the model compound [Au(bipy)(eta(2)-CH(2)[double bond, length as m-dash]CH(2))](+) show excellent agreement with the experimental findings giving in addition an estimate of a pi-back-bonding contribution higher than that of the sigma-bonding.     

New insights into the effects of self-association of the cation [Au[C(NHMe)(2)](2)](+) on its solid state structure and luminescence

Colorless [Au[C(NHMe)(2)](2)]X.H(2)O (X = Cl or Br) crystallize as dimers with Au.Au separations of 3.1231(3) A (Cl salt) and 3.1297(4) A (Br salt) between the linear, two-coordinate cations, and there is no direct interaction of Au(I) with the halide ions which are hydrogen bonded to ligand N-H groups and the water molecules. The luminescence of these dimers occurs at higher energy than that observed in extended chains of the same cation in the corresponding (PF(6))(-) and (BF(4))(-) salts and shows the important effects of aggregation on the observed luminescence.     

Intermolecular interactions in polymorphs of trinuclear gold(I) complexes: insight into the solvoluminescence of Au(I)3(MeN=COMe)3

The trinuclear complex, Au(I)3(MeN=COMe)3, which displays a number of remarkable properties including solvoluminescence, has been found to crystallize as three polymorphs. The new triclinic and monoclinic polymorphs crystallized as colorless blocks, whereas the original hexagonal polymorph formed colorless needles. These polymorphs differ in the manner in which the nearly planar molecules pack and in the nature of the aurophilic interactions between them. Each of the three polymorphs of Au(I)3(MeN=COMe)3 shows a distinctive emission spectrum, but only the original hexagonal polymorph shows the low-energy emission that is responsible for its solvoluminescence. Colorless Au(I)3(n-PentN=COMe)3 crystallized from diethyl ether as needles of an orthorhombic polymorph and blocks of a triclinic polymorph. These polymorphs differ in the orientation of the n-Pent substituents, in the orientation of the trimers with respect to one another, and in the nature of the aurophilic interactions between the molecules. Only the triclinic polymorph of Au(I)3(n-PentN=COMe)3 shows luminescence at room temperature, but it is not solvoluminescent. Colorless Au(I)3(i-PrN=COMe)3 has also been prepared and crystallographically characterized. The isopropyl groups protrude out of the plane of the nine-membered ring and prevent self-association. The closest Au...Au contact between molecules is 6.417 A. Crystalline Au(I)3(i-PrN=COMe)3 is not luminescent at room temperature.     

Thermally triggered reductive elimination of bromine from Au(III) as a path to Au(I)-based coordination polymers

Four new [AuBr(2)(CN)(2)](-)-based coordination polymers, Zn(pyz)(NCMe)(2)[AuBr(2)(CN)(2)](2) (1; pyz = pyrazine), Co(pyz)[AuBr(2)(CN)(2)](2)·H(2)O (2) and [M(bipy)(2)(AuBr(2)(CN)(2))][(n)Bu(4)N][AuBr(2)(CN)(2)](2) (bipy = 4,4'-bipyridine), where M = Co (5) and Zn (6), were synthesized and three of them structurally characterized. 1 forms 1-D chains connected by pyz ligands while isostructural 5 and 6 form 3-D frameworks via [AuBr(2)(CN)(2)](-) and bipy linkers. Aqueous suspensions of 2, 5 and 6 or their precursors in situ (preferred) were heated hydrothermally to 125 °C, triggering the reductive elimination of bromine from the Au(III) centres, which yielded the [Au(CN)(2)](-)-based coordination polymers M(pyz)[Au(CN)(2)](2), where M = Zn (3) or Co (4) and Zn(bipy)[Au(CN)(2)][Au{Br(0.68)(CN)(0.32)}CN] (7), or a mixture of cyanoaurate(I)-containing products in the case of 5 and 6. The structural characterization of 3 revealed a [Au(CN)(2)](-)/pyz-based framework similar to previously reported Cu(pyz)[Au(CN)(2)](2), whereas 7 formed an intricate network consisting of individual 2-D networks held together by AuAu interactions and featuring the rare [AuBrCN](-) unit. The kinetics of the thermally-induced reductive elimination of Br(2) from K[AuBr(2)(CN)(2)] in 1-BuOH yielded a t(?) of approx. 10 min to 4 h from 98 to 68 °C, and activation parameters of ΔH(?) = 131(15) kJ mol(-1) and ΔS(?) = 14.97(4) kJ K(-1)mol(-1), indicating that the elimination of the halogen provides the highest barrier to activation.     

Highly luminescent octanuclear Au(I)-Cu(I) clusters adopting two structural motifs: the effect of aliphatic alkynyl ligands

Reactions of the homoleptic (AuC(2)R)(n) precursors with stoichiometric amount of diphosphine ligand PPh(2)C(6)H(4)PPh(2) (P^P) and Cu(+) ions lead to an assembly of a new family of bimetallic clusters [Au(6)Cu(2)(C(2)R)(6)(P^P)(2)](2+) (type I; R=9-fluorenolyl (1), diphenylmethanolyl (2), 2,6-dimethyl-4-heptanolyl (3), 1-cyclohexanolyl (4), Cy (5), tBu (6)). In the case of R=1-cyclohexanolyl, a structurally different complex [Au(6)Cu(2)(C(2)C(6)H(11)O)(6)(P^P)(3)](2+) (7, type II) could be obtained by treatment of 4 with one equivalent of the diphosphine, while for R=isopropanolyl only the latter type of cluster [Au(6)Cu(2)(C(2)C(3)H(7)O)(6)(P^P)(3)](2+) (8) was detected. Steric bulkiness of the alkynyl ligands and O···H-O hydrogen bonding are suggested to play an important role in stabilizing the type I and type II cluster structural motif, respectively. All the complexes exhibit intense photoluminescence in solution with emission parameters that depending on the geometrical arrangement of the octanuclear metal core. The clusters 1-4 and 6 show single emission band in a blue region (469-488 nm) with maximum quantum yield of 94% (4), while structurally different 7 and 8 emit yellow-orange (590 nm) with unity quantum efficiency. The theoretical DFT calculations of the electronic structures have been carried out to demonstrate that the metal-centered triplet emission within the heterometallic core plays a key role for the observed phosphorescence.     

Solution and solid-state structure of the anion [Ag(2)[closo-CB(11)H(12)](4)](2-)

Addition of the carbene 1,3-dimesitylimidazol-2-ylidene (IMes) to a toluene solution of Ag[closo-CB(11)H(12)] results in the formation of the complex [(IMes)(2)Ag](2)[Ag(2)[closo-CB(11)H(12)](4)], the anionic component of which contains two silver(I) centers bridged by two carboranes in addition to one terminally bound carborane on each metal, in the solid-state. Comparison of the observed (11)B[(1)H] NMR chemical shifts of [(IMes)(2)Ag](2)[Ag(2)[closo-CB(11)H(12)](4)] or Ag[closo-CB(11)H(12)] with [NBu(4)][closo-CB(11)H(12)] in CD(2)Cl(2) demonstrates that the silver ion interacts significantly with the cage in solution. Theoretical investigations using the ab initio/GIAO/NMR method of [closo-CB(11)H(12)](-) and Na[closo-CB(11)H(12)] as model geometries for the silver salts support experimental evidence for these Ag...[BH] interactions in solution.     

Blue or green glowing crystals of the cation [Au{C(NHMe)2}2]+. Structural effects of anions, hydrogen bonding, and solvate molecules on the luminescence of a two-coordinate gold(I) carbene complex

Depending upon the crystallization conditions, [Au{C(NHMe) 2} 2](AsF 6) forms colorless crystals that display a blue or green luminescence. The difference involves the type of solvate molecule that is incorporated into the crystal and the structure of the chains of cations that are formed upon crystallization. The crystallographically determined structures of blue-glowing [Au{C(NHMe) 2} 2](AsF 6).0.5(benzene), blue-glowing [Au{C(NHMe) 2} 2](AsF 6).0.5(acetone), green-glowing [Au{C(NHMe) 2} 2](AsF 6).0.5(chlorobenzene), and blue-glowing, solvate-free [Au{C(NHMe) 2} 2](EF 6), E = P, As, Sb are reported. All pack with the cations forming extended columns, which may be linear or bent, but all show significant aurophilic interactions. The blue-glowing crystals have ordered stacks of cations with some variation in structural arrangement whereas the green-glowing crystals have disorder in their stacking pattern. Although there is extensive hydrogen bonding between the cations and anions in all structures, in the solvated crystals, the solvate molecules occupy channels but make no hydrogen-bonded contacts. The emission spectra of these new salts taken at 298 and 77 K are reported.