New layered materials: syntheses, structures, and optical properties of K(2)TiCu(2)S(4), Rb(2)TiCu(2)S(4), Rb(2)TiaAg(2)S(4), Cs(2)TiAg(2)sS(4), and Cs(2)TiCu(2)Se(4)

The new compounds K(2)TiCu(2)S(4), Rb(2)TiCu(2)S(4), Rb(2)TiAg(2)S(4), Cs(2)TiAg(2)S(4), and Cs(2)TiCu(2)Se(4) have been synthesized by the reactions of A(2)Q(3) (A = K, Rb, Cs; Q = S, Se) with Ti, M (M = Cu or Ag), and Q at 823 K. The compounds Rb(2)TiCu(2)S(4), Cs(2)TiAg(2)S(4), and Cs(2)TiCu(2)Se(4) are isostructural. They crystallize with two formula units in space group P4(2)/mcm of the tetragonal system in cells of dimensions a = 5.6046(4) A, c = 13.154(1) A for Rb(2)TiCu(2)S(4), a =6.024(1) A, c = 13.566(4) A for Cs(2)TiAg(2)S(4), and a =5.852(2) A, c =14.234(5) A for Cs(2)TiCu(2)Se(4) at 153 K. Their structure is closely related to that of Cs(2)ZrAg(2)Te(4) and comprises [TiM(2)Q(4)(2)(-)] layers, which are separated by alkali metal atoms. The [TiM(2)Q(4)(2)(-)] layer is anti-fluorite-like with both Ti and M atoms tetrahedrally coordinated to Q atoms. Tetrahedral coordination of Ti(4+) is rare in the solid state. On the basis of unit cell and space group determinations, the compounds K(2)TiCu(2)S(4) and Rb(2)TiAg(2)S(4) are isostructural with the above compounds. The band gaps of K(2)TiCu(2)S(4), Rb(2)TiCu(2)S(4), Rb(2)TiAg(2)S(4), and Cs(2)TiAg(2)S(4) are 2.04, 2.19, 2.33, and 2.44 eV, respectively, as derived from optical measurements. From band-structure calculations, the optical absorption for an A(2)TiM(2)Q(4) compound is assigned to a transition from an M d and Q p valence band (HOMO) to a Ti 3d conduction band.     

Nanostructured Ti(1-x)S(x)O(2-y)N(y) heterojunctions for efficient visible-light-induced photocatalysis

Highly visible-light-active S,N-codoped anatase-rutile heterojunctions are reported for the first time. The formation of heterojunctions at a relatively low temperature and visible-light activity are achieved through thiourea modification of the peroxo-titania complex. FT-IR spectroscopic studies indicated the formation of a Ti(4+)-thiourea complex upon reaction between peroxo-titania complex and thiourea. Decomposition of the Ti(4+)-thiourea complex and formation of visible-light-active S,N-codoped TiO(2) heterojunctions are confirmed using X-ray diffraction, Raman spectroscopy, transmission electron microscopy, and UV/vis spectroscopic studies. Existence of sulfur as sulfate ions (S(6+)) and nitrogen as lattice (N-Ti-N) and interstitial (Ti-N-O) species in heterojunctions are identified using X-ray photoelectron spectroscopy (XPS) and FT-IR spectroscopic techniques. UV-vis and valence band XPS studies of these S,N-codoped heterojunctions proved the fact that the formation of isolated S 3p, N 2p, and Π* N-O states between the valence and conduction bands are responsible for the visible-light absorption. Titanium dioxide obtained from the peroxo-titania complex exists as pure anatase up to a calcination temperature as high as 900 °C. Whereas, thiourea-modified samples are converted to S,N-codoped anatase-rutile heterojunctions at a temperature as low as 500 °C. The most active S,N-codoped heterojunction 0.2 TU-TiO(2) calcined at 600 °C exhibits a 2-fold and 8-fold increase in visible-light photocatalytic activities in contrast to the control sample and the commercial photocatalyst Degussa P-25, respectively. It is proposed that the efficient electron-hole separation due to anatase to rutile electron transfer is responsible for the superior visible-light-induced photocatalytic activities of S,N-codoped heterojunctions.     

Exploratory synthesis in molten salts: role of flux basicity in the stabilization of the complex thiogermanates Cs(4)Pb(4)Ge(5)S(16), K(2)PbGe(2)S(6), and K(4)Sn(3)Ge(3)S(14)

The influence of the Lewis basicity of alkali polysulfide fluxes (A(2)S(x)) (A = alkali) as a function of x on the respective reactivities of Pb and Sn with Ge was studied and found to be strong. Cs(4)Pb(4)Ge(5)S(16), K(2)PbGe(2)S(6), and K(4)Sn(3)Ge(3)S(14) could be prepared only under low basicity with S/A(2)S ratios of > or =11. These compounds display complex frameworks and are semiconductors. Cs(4)Pb(4)Ge(5)S(16) is luminescent with red emission.     

Syntheses and structures of the infinite chain compounds Cs(4)Ti(3)Se(13), Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14)

The alkali metal/group 4 metal/polychalcogenides Cs(4)Ti(3)Se(13), Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14) have been synthesized by means of the reactive flux method at 823 or 873 K. Cs(4)Ti(3)Se(13) crystallizes in a new structure type in space group C(2)(2)-P2(1) with eight formula units in a monoclinic cell at T = 153 K of dimensions a = 10.2524(6) A, b = 32.468(2) A, c = 14.6747(8) A, beta = 100.008(1) degrees. Cs(4)Ti(3)Se(13) is composed of four independent one-dimensional [Ti(3)Se(13)(4-)] chains separated by Cs(+) cations. These chains adopt hexagonal closest packing along the [100] direction. The [Ti(3)Se(13)(4-)] chains are built from the face- and edge-sharing of pentagonal pyramids and pentagonal bipyramids. Formal oxidation states cannot be assigned in Cs(4)Ti(3)Se(13). The compounds Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14) crystallize in the K(4)Ti(3)S(14) structure type with four formula units in space group C(2)(h)()(6)-C2/c of the monoclinic system at T = 153 K in cells of dimensions a = 21.085(1) A, b = 8.1169(5) A, c = 13.1992(8) A, beta = 112.835(1) degrees for Rb(4)Ti(3)S(14);a = 21.329(3) A, b = 8.415(1) A, c = 13.678(2) A, beta = 113.801(2) degrees for Cs(4)Ti(3)S(14); a = 21.643(2) A, b = 8.1848(8) A, c = 13.331(1) A, beta = 111.762(2) degrees for Rb(4)Hf(3)S(14); a = 22.605(7) A, b = 8.552(3) A, c = 13.880(4) A, beta = 110.919(9) degrees for Rb(4)Zr(3)Se(14); a = 22.826(5) A, b = 8.841(2) A, c = 14.278(3) A, beta = 111.456(4) degrees for Cs(4)Zr(3)Se(14); and a = 22.758(5) A, b = 8.844(2) A, c = 14.276(3) A, beta = 111.88(3) degrees for Cs(4)Hf(3)Se(14). These A(4)M(3)Q(14) compounds (A = alkali metal; M = group 4 metal; Q = chalcogen) contain hexagonally closest-packed [M(3)Q(14)(4-)] chains that run in the [101] direction and are separated by A(+) cations. Each [M(3)Q(14)(4-)] chain is built from a [M(3)Q(14)] unit that consists of two MQ(7) pentagonal bipyramids or one distorted MQ(8) bicapped octahedron bonded together by edge- or face-sharing. Each [M(3)Q(14)] unit contains six Q(2)(2-) dimers, with Q-Q distances in the normal single-bond range 2.0616(9)-2.095(2) A for S-S and 2.367(1)-2.391(2) A for Se-Se. The A(4)M(3)Q(14) compounds can be formulated as (A(+))(4)(M(4+))(3)(Q(2)(2-))(6)(Q(2-))(2).     

Accumulating resampling (modulation) in comprehensive two-dimensional capillary GC (GC x GC)

During each sampling period, an accumulating resampler (modulator) in comprehensive 2-D chromatography accumulates all eluite from the first-dimension column and reinjects the whole or a portion of the accumulated material into the second-dimension column. The detrimental effect of the resampling on peak capacity of a 2-D separation comes from the broadening of the peaks along the first-dimension due to the resampling itself and due to the subsequent peak reconstruction. Sampling density (rho(S)) of resampling is the number of sampling periods per standard deviation of a peak at the outlet of the first-dimension column. It is shown that a simple formula describes the peak broadening as a function of rho(S) at any (even practically too low or too high) rho(S), for the peaks of any (not necessarily Gaussian) shape, for a wide class of peak reconstruction techniques, and for any 2-D separation (GC x GC, LC x LC, etc.). In capillary GC x GC, optimal rho(S) (rho(S,Opt)) depends on the type of the peak reconstruction and on the degree of the gas decompression along the second-dimension column. When reconstructing using linear interpolation, rho(S,Opt) = 0.7 at large and rho(S,Opt) = 0.5 at small gas decompression. The choice of exact optimal conditions is not critical. Thus, two-fold departure of actual rho(S) from rho(S,Opt) in either direction (under- or oversampling) causes only 10% drop in the net peak capacity of GC x GC. The quantitative effect of a much greater undersampling is also evaluated.     

Extending the coordination chemistry of molecular P(4)S(3): the polymeric Ag(P(4)S(3))(+) and Ag(P(4)S(3))(2)(+) cations

Upon reacting P(4)S(3) with AgAl(hfip)(4) and AgAl(pftb)(4) [hfip = OC(H)(CF(3))(2); pftb = OC(CF(3))(3)], the compounds Ag(P(4)S(3))Al(hfip)(4) 1 and Ag(P(4)S(3))(2)(+)[Al(pftb)(4)](-) 2 formed in CS(2) (1) or CS(2)/CH(2)Cl(2) (2) solution. Compounds 1 and 2 were characterized by single-crystal X-ray structure determinations, Raman and solution NMR spectroscopy, and elemental analyses. One-dimensional chains of [Ag(P(4)S(3))(x)](infinity) (x = 1, 1; x = 2, 2) formed in the solid state with P(4)S(3) ligands that bridge through a 1,3-P,S, a 2,4-P,S, or a 3,4-P,P eta(1) coordination to the silver ions. Compound 2 with the least basic anion contains the first homoleptic metal(P(4)S(3)) complex. Compounds 1 and 2 also include the long sought sulfur coordination of P(4)S(3). Raman spectra of 1 and 2 were assigned on the basis of DFT calculations of related species. The influence of the silver coordination on the geometry of the P(4)S(3) cage is discussed, additionally aided by DFT calculations. Consequences for the frequently observed degradation of the cage are suggested. An experimental silver ion affinity scale based on the solid-state structures of several weak Lewis acid base adducts of type (L)AgAl(hfip)(4) is given. The affinity of the ligand L to the silver ion increases according to P(4) < CH(2)Cl(2) < P(4)S(3) < S(8) < 1,2-C(2)H(4)Cl(2) < toluene.     

NiN(2)S(2) complexes as metallodithiolate ligands to Rh(I), Rh(II) and Rh(III)

Three molecular structures are reported which utilize the NiN(2)S(2) ligands -, (bis(mercaptoethyl)diazacyclooctane)nickel and -', bis(mercaptoethyl)diazacycloheptane)nickel, as metallodithiolate ligands to rhodium in oxidation states i, ii and iii. For the Rh(I) complex, the NiN(2)S(2) unit behaves as a bidentate ligand to a square planar Rh(I)(CO)(PPh(3))(+) moiety with a hinge or dihedral angle (defined as the intersection of NiN(2)S(2) and S(2)Rh(C)(P) planes) of 115 degrees . Supported by -' ligands, the Rh(II) oxidation state occurs in a dirhodium C(4) paddlewheel complex wherein four NiN(2)S(2) units serve as bidentate bridging ligands to two singly-bonded Rh(II) ions at 2.893(8) A apart. A compilation of the remarkable range of M-M distances in paddlewheel complexes which use NiN(2)S(2) complexes as paddles is presented. The Rh(III) state is found as a tetrametallic [Rh(-')(3)](3+) cluster, roughly shaped like a boat propeller and structurally similar to tris(bipyridine)metal complexes.     

A first-principles study of (R)- and (S)-PPA Molecules on Cu(111)

The adsorption of (R)- and (S)-2-phenylpropionamide (PPA, C(9)H(11)ON) molecules on a Cu(111) surface has been investigated using the density functional method with supercell models. The adsorption orientations of both (R)- and (S)-PPA molecules on the surface are the same: the phenyl rings are approximately parallel to the Cu(111) surface and positioned in the hollow sites, the amino and methyl groups occupy two-bridge sites, and the carbonyl occupies the top site. After the adsorption, the bond lengths in the two enantiomers are almost unchanged, but the changes for two dihedral angles show differences, especially for (R)-PPA molecule. The first angles between the (N,C9,C7) plane and the (C9,C7,C6) plane are 19.4 and 0.7 degrees for (R)- and (S)-PPA molecules, respectively, and the second angles between the (C8,C7,C6) plane and the (C7,C6,C5) plane are 74.8 and 0.4 degrees for (R)- and (S)-PPA molecules, respectively. The adsorption energies of (R)- and (S)-PPA molecules are calculated to be -34 and -26 kJ mol(-1), respectively. The simulated scanning tunneling microscopy (STM) images of (R)- and (S)-PPA molecules on the Cu(111) surface display different features and are coincident with the experimental ones. The interaction between the adsorption molecule and the metal surface is found to be responsible for the discrimination of (R)- and (S)-PPA molecules on the surface.     

PHOTOSENSITIZED REACTIONS OF POLY(U) WITH TRIS(2,2'' BIPYRIDYL)RUTHENIUM(II) AND PEROXYDISULFATE

The reactions of polyuridylic acid [poly(U)] with Ru(bpy)3(3+) [Ru(III)] and SO4.-, following UV and visible light irradiation of Ru(bpy)3(2+) [Ru(II)] in the presence of S2O8(2-), were studied in an argon-saturated aqueous solution using time-resolved absorption and conductivity methods. The kinetics of the Ru(III) conversion to Ru(II) in the presence of poly(U) was monitored spectroscopically either in the absence of SO4.- [rapid mixing with Ru(III)] or in its presence (after laser flash excitation, lambda exc = 353 nm). The conversion of Ru(III) to Ru(II) is complete at a [nucleotide]/[sensitizer] (N/S) ratio greater than or equal to 10 (rate constant k = 12 s-1) for rapid mixing and at N/S greater than or equal to 6 (k = 15 s-1 at N/S = 10) after laser pulsing. Conductivity measurements following the laser pulse revealed a fast conductivity increase (risetime less than 10 micros), due to the formation of charged species and protons. A slower increase in the 0.1-0.5 s range was observed for poly(U) but it is considerably smaller for poly(dU) and absent in uracil containing monounits. The slow increase is unaffected by pH changes in the 3.5-7 range, markedly reduced in the 7-9 range and is replaced by a slight decrease in conductivity in buffered solutions. An explanation is that poly(U)-bound excited Ru(II) reacts with S2O8(2-) forming Ru(III) and SO4.- as oxidizing species both of which react with poly(U) bases. The resulting base radicals react with Ru(III) or the ligands in the ruthenium complex, producing protons which give rise to the slow conductivity increase (k = 15 s-1 at N/S = 10). The formation of single-strand breaks and the ensuing release of condensed counterions does not appear to contribute significantly to the slow conductivity signal. At N/S less than 10 the observed rate and extent of Ru(III)--Ru(II) conversion and of the slow proton production vary markedly with the N/S ratio.     

Interconversion of (S)-glutamate and (2S,3S)-3-methylaspartate: a distinctive B(12)-dependent carbon-skeleton rearrangement

The interconversion of (S)-glutamate and (2S,3S)-3-methylaspartate catalyzed by B(12)-dependent glutamate mutase is discussed using results from high-level ab initio molecular orbital calculations. Evidence is presented regarding the possible role of coenzyme-B(12) in substrate activation and product formation via radical generation. Calculated electron paramagnetic resonance parameters support experimental evidence for the involvement of substrate-derived radicals and will hopefully aid the future detection of other important radical intermediates. The height of the rearrangement barrier for a fragmentation-recombination pathway, calculated with a model that includes neutral amino and carboxylic acid substituents in the migrating glycyl group, supports recent experimental evidence for the interconversion of (S)-glutamate and (2S,3S)-3-methylaspartate through such a pathway. Our calculations suggest that the enzyme may facilitate the rearrangement of (S)-glutamate through (partial) proton-transfer processes that control the protonation state of substituents in the migrating group.     

Structure and magnetic properties of (meso-tetraphenylporphinato)manganese(III) bis(dithiolato)nickelates

The crystal structures of [MnTPP]{Ni[S2C2H(CN)]2} [MnTPP = (meso-tetraphenylporphinato)manganese(III)] and [MnTPP]{Ni[S2C2(CN)2]2} have been determined. These salts possess trans-mu-coordination of S = 1/2 {Ni[S2C2H(CN)]2}*- and {Ni[S(2)C(2)(CN)(2)](2)}*- to Mn(III) and form parallel 1-D coordination polymer chains exhibiting nu(CN) at 2210 and 2200 and 2220 and 2212 cm(-1), respectively. The bis(dithiolato) monoanions are planar and bridge two cations with MnN distances of 2.339(16), and 2.394(3) A, respectively, which are comparable to related MnN distances observed for [MnTPP][TCNE].x(solvates). In addition, [MnTP'P]{Ni[S2C2(CN)2]2} {H2TP'P = meso-tetrakis[3,5-di-tert-butyl-4-hydroxyphenyl)porphyrin] and [MnTP'P(OH2)]{Ni[S2C2(CN)2]2} were prepared. The latter forms isolated paramagnetic ions. The room-temperature values of chiT for 1-D [MnTPP]{Ni[S2C2H(CN)]2}, [MnTPP]{Ni[S2C2(CN)2]2}, and [MnTP'P]{Ni[S2C2(CN)2]2} are 2.55, 3.28, and 2.86 emu K/mol, respectively. Susceptibility (chi) measurements between 2 and 300 K reveal weak antiferromagnetic interactions with theta= -5.9 and -0.2 K for [MnTPP]{Ni[S(2)C(2)H(CN)](2)} and [MnTPP]{Ni[S2C2(CN)2]2}, respectively, and stronger antiferromagnetic coupling of -50 K for [MnTP'P]{Ni[S2C2(CN)2]2} from fits of chi(T) to the Curie-Weiss law. The 1-D intrachain coupling, J(intra), of [MnTPP]{Ni[S2C2H(CN)]2} and [MnTPP]{Ni[S2C2(CN)2]2} was determined from modeling chiT(T) by the Seiden expression (H = -2JSi.Sj) with J/kB = -8.00 K (-5.55 cm(-1); -0.65 meV) for [MnTPP]{Ni[S2C2H(CN)]2}, J/kB = -3.00 K (-2.08 cm(-1); -0.25 meV) for [MnTP'P]{Ni[S2C2(CN)2]2}, and J/kB = -122 K (-85 cm(-1)) for [MnTP'P]{Ni[S2C2(CN)2]2}. These observed negative J(intra)/kB values are indicative of antiferromagnetic coupling. These materials order as ferrimagnets at 5.5, 2.3, and 8.0 K, for [MnTPP]{Ni[S2C2H(CN)]2}, [MnTPP]{Ni[S2C2(CN)2]2}, and [MnTP'P]{Ni[S2C2(CN)2]2}, respectively, based upon the temperature at which maximum in the 10 Hz chi'(T) data occurs. [MnTP'P]{Ni[S2C2(CN)2]2} has a coercivity of 17,700 Oe and remanent magnetizations of 7250 emu Oe/mol at 2 K and 17 Oe and 850 emu Oe/mol at 5 K; hence, upon cooling it goes from being a soft magnet to being a very hard magnet.     

Polydentate N(2)S(2)O and N(2)S(2)O(2) Ligands as Alcoholic Derivatives of (N,N'-Bis(2-mercaptoethyl)-1,5-diazacyclooctane)nickel(II) and (N,N'-Bis(2-mercapto-2-methylpropane)-1,5-diazacyclooctane)nickel(II)

The synthesis, structural characterization, spectroscopic, and electrochemical properties of N(2)S(2)-ligated Ni(II) complexes, (N,N'-bis(2-mercaptoethyl)-1,5-diazacyclooctane)nickel(II), (bme-daco)Ni(II), and (N,N'-bis(2-mercapto-2-methylpropane)1,5-diazacyclooctane)nickel(II), (bme-daco)Ni(II), derivatized at S with alcohol-containing alkyl functionalities, are described. Reaction of (bme-daco)Ni(II) with 2-iodoethanol afforded isomers, (N,N'-bis(5-hydroxy-3-thiapentyl)-1,5-diazacyclooctane-O,N,N',S,S')halonickel(II) iodide (halo = chloro or iodo), 1, and (N,N'-bis(5-hydroxy-3-thiapentyl)-1,5-diazacyclooctane-N,N',S,S')nickel(II) iodide, 2, which differ in the utilization of binding sites in a potentially hexadentate N(2)S(2)O(2) ligand. Blue complex 1 contains nickel in an octahedral environment of N(2)S(2)OX donors; X is best modeled as Cl. It crystallizes in the monoclinic space group P2(1)/n with a = 12.580(6) ?, b = 12.291(6) ?, c = 13.090(7) ?, beta = 97.36(4) degrees, and Z = 4. In contrast, red complex 2 binds only the N(2)S(2) donor set forming a square planar nickel complex, leaving both -CH(2)CH(2)OH arms dangling; the iodide ions serve strictly as counterions. 2 crystallizes in the orthorhombic space group Pca2(1) with a = 15.822(2) ?, b = 13.171(2) ?, c = 10.0390(10) ?, and Z = 4. Reaction of (bme-daco)Ni(II) with 1,3-dibromo-2-propanol affords another octahedral Ni species with a N(2)S(2)OBr donor set, ((5-hydroxy-3,7-dithianonadiyl)-1,5-diazacyclooctane-O,N,N',S,S')bromonickel(II) bromide, 3. Complex 3 crystallizes in the orthorhombic space group Pca2(1) with a = 15.202(5) ?, b = 7.735(2) ?, c = 15.443(4) ?, and Z = 4. Complex 4.2CH(3)CN was synthesized from the reaction of (bme-daco)Ni(II) with 1,3-dibromo-2-propanol. It crystallizes in the monoclinic space group P2/c with a = 20.348(5) ?, b = 6.5120(1) ?, c = 20.548(5) ?, and Z = 4.     

Preparation and X-ray structures of Cu(I), Ni(II), and Pd(II) (N,S) complexes of the monoanion [(tBuN)(S)P(mu-N(t)Bu)2P(S)(NH(t)Bu)]- and a Pt(II) (S,S') complex of the dianion [((t)BuN)(S)P(mu-N(t)Bu)2P(S)(N(t)Bu)]2-

The metathetical reactions of the lithium derivative of the monoanion [((t)BuN)(S)P(mu-N(t)Bu)(2)P(S)(NH(t)Bu)](-) (L) with CuCl/PPh(3), NiCl(2)(PEt(3))(2), PdCl(2)L'(2) (L' = PhCN, PPh(3)), and PtCl(2)(PEt(3))(2) produced the complexes (PPh(3))CuL (5), NiL(2) (6), PdCl(L)(PPh(3)) (7), PdL(2) (8), and Pt(PEt(3))(2)[((t)BuN)(S)P(mu-N(t)Bu)(2)P(S)(N(t)Bu)] (9). The X-ray structures of 5, 6, and 8 reveal a N,S-coordination for the chelating monoanion L with the metal centers in trigonal planar, tetrahedral, and square planar environments, respectively. By contrast, the dianionic ligand in the square planar Pt(II) complex 9 is S,S'-chelated to the metal center. (31)P NMR spectra readily distinguish between the N,S and S,S' bonding modes, and, on that basis, N,S chelation is inferred for the Pd(II) complex 7. Crystal data: 5, monoclinic, P2(1)/c, a = 19.175(4) A, b = 20.331(4) A, c = 10.017(6) A, beta = 91.79(3) degrees, V = 3903(2) A(3), and Z = 4; 6, orthorhombic, Pbcn, a = 14.298(5) A, b = 15.333(5) A, c = 24.378(5) A, beta = 90.000(5) degrees, V = 5344(3) A(3), and Z = 4; 8, monoclinic, P2(1)/n, a = 13.975(3) A, b = 14.283(3) A, c = 15.255(4) A, beta = 116.565(18) degrees, V = 2723.5(11) A(3), and Z = 2; 9, monoclinic, P2(1)/n, a = 12.479(6) A, b = 21.782(7) A, c = 17.048(5) A, beta = 100.30(3) degrees, V = 4559(3) A(3), and Z = 4.     

Chemical reactions inside structured nano-environment: S(N)2 vs. E2 reactions for the F(-) + CH(3)CH(2)Cl system

A new receptor for S(N)2 transition states, named NPTROL, is proposed. This molecule has a cavity and four hydroxyl groups that are able to interact with ionic S(N)2 and E2 transition states. Its catalytic effect and selectivity was investigated through high level ab initio calculations using the fluoride ion plus ethyl chloride in DMSO solution as a model system. Calculations at the ONIOM[CCSD(T)/6-311+G(2df,2p)?:?MP2/BASIS1] level of theory and solvent effects, included through a continuum solvation model, indicate that NPTROL is able to catalyze the S(N)2 pathway and has an inverse effect on the E2 pathway. Inside the NPTROL cavity, the ΔG(?) for the S(N)2 transition state is 5.00 kcal mol(-1) lower than that for E2, and as a consequence this reaction becomes highly selective toward the S(N)2 product.     

Novel quaternary lanthanum bismuth sulfides Pb(2)La(x)Bi(8-x)(S(14)), Sr(2)La(x)Bi(8-x)S(14), and Cs(2)La(x)Bi(10-x)S(16) with complex structures

The compounds Pb(2)La(x)Bi(8-x)S(14) (I), Sr(2)La(x)Bi(8-x)S(14) (II), and Cs(2)La(x)Bi(10-x)S(16) (III) were synthesized from the corresponding elements or binary sulfides at temperatures above 850 degrees C. Compounds I and II are isostructural, forming a new structure type, while the structure of III is related to the structure of the mineral kobellite. All compounds crystallize in the orthorhombic space group Pnma (No. 62) with a = 21.2592(4) A, b = 4.0418(1) A, c = 28.1718(3) A, Z = 4 for I, a = 21.190(1) A, b = 4.0417(2) A, c = 28.285(2) A, Z = 4 for II and a = 34.893(4) A, b = 4.0697(4) A, c = 21.508(2) A, Z = 4 for III. All compounds exhibit mixed site occupancy between Bi and La. Furthermore, I and II exhibit disorder between the divalent atom (Sr or Pb) and/or La and/or Bi. The structures of I and II consist of thin walls made of two metal-atom-thick NaCl-type blocks running in two opposite directions in the ac plane, forming rhombus-shaped tunnels. These tunnels are filled with Bi(2)Te(3)-type fragments. In the points where the walls intersect they form Gd(2)S(3)-type fragments. The structure of III consists of a complex three-dimensional framework with Cs-filled tunnels. All compounds are semiconductors with band gaps around 1.0 eV, and they melt around 740-860 degrees C.     

Rhenium(V) Oxo Complexes of Novel N(2)S(2) Dithiourea (DTU) Chelate Ligands: Synthesis and Structural Characterization

The compounds RNHC(=S)NH(CH(2))(n)()NHC(=S)NHR were prepared in a search for new, relatively small N(2)S(2) ligands. These dithiourea (DTU) ligands are the first chelates containing two potentially bidentate thiourea moieties. A one-step reaction of 1,3-diaminopropane (1) with aryl or alkyl isothiocyanates or of 1,2-diaminoethane (2) with phenyl isothiocyanate afforded the target ligands in excellent yields (95-98%). The Re(V)=O complexes of RNHC(=S)NH(CH(2))(3)NHC(=S)NHR ligands were obtained through ligand exchange reactions with Re(V) precursors. The chemistry required neither protection of the sulfur atoms for ligand synthesis nor deprotection prior to metal complexation. The structure of (1-phenyl-3-(3-phenylthioureido)propyl]thioureato)oxorhenium(V) (7a), determined by X-ray diffraction methods, revealed the expected pseudo-square-pyramidal geometry with an N(2)S(2) basal and an apical oxo donor set. Both coordinated N's (N(c)) were deprotonated. One uncoordinated N (N(u)) was deprotonated, producing a neutral complex containing an unexpected new type of dianionic, four-membered N,S chelate. In the crystal, the N(u) atoms, N(3)H and N(4), of one complex each formed an H-bond with N(4) and N(3)H, respectively, of a symmetry-related complex. The N(c)-C-S bond angles (106.1(6) and 101.5(6) degrees ) were severely distorted from the 120 degrees expected for an sp(2)-hybridized C. However, these small bite angles and the large N-Re-N bond angle (86.1(3) degrees ) allowed for the formation of two four-membered chelate rings with normal Re-N and Re-S bond distances. Attempts to prepare complexes with the PhNHC(=S)NH(CH(2))(2)NHC(=S)NHPh ligand were unsuccessful. These results suggest that a central five-membered chelate ring is too small to accommodate bidentate coordination of both thiourea moieties. NMR studies in methanol established that the neutral complex with one uncoordinated N deprotonated was the favored form in neutral and basic solutions. However, under acidic conditions, a cationic form with both uncoordinated N's protonated was favored.     

Diverse evolution of [[Ph(2)P(CH(2))(n)PPh(2)]Pt(mu-S)(2)Pt[Ph(2)P(CH(2))(n)PPh(2)]] (n = 2, 3) metalloligands in CH(2)Cl(2)

The nucleophilicity of the [Pt(2)S(2)] core in [[Ph(2)P(CH(2))(n)PPh(2)]Pt(mu-S)(2)Pt[Ph(2)P(CH(2))(n)PPh(2)]] (n = 3, dppp (1); n = 2, dppe (2)) metalloligands toward the CH(2)Cl(2) solvent has been thoroughly studied. Complex 1, which has been obtained and characterized by X-ray diffraction, is structurally related to 2 and consists of dinuclear molecules with a hinged [Pt(2)S(2)] central ring. The reaction of 1 and 2 with CH(2)Cl(2) has been followed by means of (31)P, (1)H, and (13)C NMR, electrospray ionization mass spectrometry, and X-ray data. Although both reactions proceed at different rates, the first steps are common and lead to a mixture of the corresponding mononuclear complexes [Pt[Ph(2)P(CH(2))(n)PPh(2)](S(2)CH(2))], n = 3 (7), 2 (8), and [Pt[Ph(2)P(CH(2))(n)PPh(2)]Cl(2)], n = 3 (9), 2 (10). Theoretical calculations give support to the proposed pathway for the disintegration process of the [Pt(2)S(2)] ring. Only in the case of 1, the reaction proceeds further yielding [Pt(2)(dppp)(2)[mu-(SCH(2)SCH(2)S)-S,S']]Cl(2) (11). To confirm the sequence of the reactions leading from 1 and 2 to the final products 9 and 11 or 8 and 10, respectively, complexes 7, 8, and 11 have been synthesized and structurally characterized. Additional experiments have allowed elucidation of the reaction mechanism involved from 7 to 11, and thus, the origin of the CH(2) groups that participate in the expansion of the (SCH(2)S)(2-) ligand in 7 to afford the bridging (SCH(2)SCH(2)S)(2-) ligand in 11 has been established. The X-ray structure of 11 is totally unprecedented and consists of a hinged [(dppp)Pt(mu-S)(2)Pt(dppp)] core capped by a CH(2)SCH(2) fragment.     

Structural variability in Ag(I) and Cu(I) coordination polymers with thioether-functionalized bis(pyrazolyl)methane ligands

We present here two ligand classes based on a bis(pyrazolyl)methane scaffold functionalized with a rigid (-Ph-S-Ph) or flexible (-CH(2)-S-Ph) thioether function: L(R)PhS (R = H, Me) and L(R)CH(2)S (R = H, Me, iPr). The X-ray molecular structures of Ag(I) and Cu(I) binary complexes with L(R)PhS or L(R)CH(2)S using different types of counterions (BF(4)(-), PF(6)(-), and CF(3)SO(3)(-)) are reported. In these complexes, the ligands are N(2) bound on a metal center and bridge on a second metal with the thioether group. In contrast, when using triphenylphosphine (PPh(3)) as an ancillary ligand, mononuclear ternary complexes [M(L)PPh(3)](+) (M = Cu(I), Ag(I); L = L(R)PhS, L(R)CH(2)S) are formed. In these complexes, the more flexible ligand type, L(R)CH(2)S, is able to provide the N(2)S chelation, whereas the more rigid L(R)PhS ligand class is capable of chelating only N(2) because the thioether function preorganized, as it did in the coordination polymers, to point away from the metal center. Rigid potential-energy surface scans were performed by means of density functional theory (DFT) calculations (B3LYP/6-31+G) on the two representative ligands, L(H)PhS and L(H)CH(2)S. The surface scans proved that the thioether function is preferably oriented on the opposite side of the bispyrazole N(2) chelate system. These results confirm that both ligand classes are suitable components for the construction of coordination polymers. Nevertheless, the methylene group that acts as a spacer in L(H)CH(2)S imparts an inherent flexibility to this ligand class so that the conformation responsible for the N(2)S chelation is energetically accessible.     

Tris(dimethylamino)oxosulfonium difluorotrimethylsilicate, (Me(2)N)(3)SO(+)Me(3)SiF(2)(-) (TAOS Fluoride)

In the OSF(4)/Me(2)NSiMe(3) system besides the long known Me(2)NS(O)F(3) only the trisubstituted derivative is isolated as (Me(2)N)(3)SO(+)Me(3)SiF(2)(-) (3). Similar to (Me(2)N)(3)S(+)Me(3)SiF(2)(-) compound 3 is an excellent fluoride ion donor. With AsF(5) and HF the corresponding hexafluoroarsenate (Me(2)N)(3)SO(+)AsF(6)(-) (4) and the hydrogen bifluoride (Me(2)N)(3)SO(+)HF(2)(-) (5) are formed in almost quantitative yield. X-ray structure determinations of 3-5 surprisingly showed two different types of structures for the cation. In 3 and 5 this cation has C(3) symmetry, while in the hexafluoroarsenate 4 a (Me(2)N)(3)S(+)-like structure with C(s)() symmetry is determined. The experimental results for (Me(2)N)(3)SO(+) and (Me(2)N)(3)S(+) are compared with theoretical calculations for these cations and their isoelectronic neutral counterparts, the phosphorus amides (Me(2)N)(3)PO and (Me(2)N)(3)P, respectively.