Silylene hydride complexes of molybdenum with silicon-hydrogen interactions: neutron structure of (eta(5)-C(5)Me(5))(Me(2)PCH(2)CH(2)PMe(2))Mo(H)(SiEt(2))

Reduction of CpMoCl(4) with 3.1 equiv of Na/Hg amalgam (1.0% w/w) in the presence of 1 equiv of dmpe and 1 equiv of trimethylphosphine afforded the molybdenum(II) chloride complex Cp(dmpe)(PMe(3))MoCl (1) (Cp = 1,2,3,4,5-pentamethylcyclopentadienyl, dmpe = 1,2-bis(dimethylphosphino)ethane). Alkylation of 1 with PhCH(2)MgCl proceeded in high yield to liberate PMe(3) and give the 18-electron pi-benzyl complex Cp(dmpe)Mo(eta(3)-CH(2)Ph) (2). Variable temperature NMR experiments provided evidence that 2 is in equilibrium with its 16-electron eta(1)-benzyl isomer [Cp(dmpe)Mo(eta(1)-CH(2)Ph)]. This was further supported by reaction of 2 with CO to yield the carbonyl benzyl complex Cp(dmpe)(CO)Mo(eta(1)-CH(2)Ph) (3). Complex 2 was found to react with disubstituted silanes H(2)SiRR' (RR' = Me(2), Et(2), MePh, and Ph(2)) to form toluene and the silylene complexes Cp(dmpe)Mo(H)(SiRR') (4a: RR' = Me(2); 4b: RR' = Et(2); 4c: RR' = MePh; 4d: RR' = Ph(2)). Reactions of 2 with monosubstituted silanes H(3)SiR (R = Ph, Mes, Mes = 2,4,6-trimethylphenyl) produced rare examples of hydrosilylene complexes Cp(dmpe)Mo(H)Si(H)R (5a: R = Ph; 5b: R = Mes; 5c: R = CH(2)Ph). Reactivity of complexes 4a-c and 5a-d is dominated by 1,2-hydride migration from metal to silicon, and these complexes possess H.Si bonding interactions, as supported by spectroscopic and structural data. For example, the J(HSi) coupling constants in these species range in value from 30 to 48 Hz and are larger than would be expected in the absence of H.Si bonding. A neutron diffraction study on a single crystal of diethylsilylene complex 4b unequivocally determined the hydride ligand to be in a bridging position across the molybdenum-silicon bond (Mo-H 1.85(1) A, Si-H 1.68(1) A). The synthesis and reactivity properties of these complexes are described in detail.     

Trimethylphosphine complexes of tungsten(O) and (IV). X-ray crystal structures of trimethylphosphine tris (phenylacetylene) tungsten(O); bis(trimethylphosphine) tetrakis (methylisocyanide) tungsten(O), and oxodichlorotris (trimethylphosphine) tungsten (IV)

The reduction of WCl₄(PMe₃)₃ by sodium amalgam in presence of phenylacetylene gives W(PMe₃)(PhCCH)₃ (A). Reduction in presence of methylisocyanide gives W(PMe₃)₂(MeNC)₄ (B), while in presence of excess PMe₃ in tetrahydrofuran under hydrogen, WH₂Cl₂(PMe₃)₄ (C) is formed. The reaction of WCl₂(PMe₃)₄ with methanol in tetrahydrofuran gives mixtures of WH₂Cl₂(PMe₃)₄ and WOC1₂(PMe₃)₃ (D).The structures of A, B, and D have been determined by X-ray diffraction.     

Micro-determination of As(V), V(V), Mo(VI), W(VI) in the presence of Cu(II), Ni(II) and Zn(II)

A rapid procedure is described for the separation and determination of 0.025 mg to 1.0 mg quantities of As(V), V(V), Mo(VI) and W(VI) from small quantities of Cu(II), Ni(II), and Zn(II) using silica gel as the selective sorbent for the cations. The individual anionic components, which remain in the supernatant solution after separation from the cations, are determined by colorimetric methods. The complete recovery of As(V) in supernatant solution has also been tested radiometrically using⁷⁶As as the radioactive indicator. The sorbed cations after extraction with dilute hydrochloric acid are determined by EDTA titrations.     

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).     

Copper(II), nickel(II), cobalt(II), manganese(II), iron(III) and oxovanadium(IV) complexes of biacetylmonoquinolylhydrazone (BAMQH)

Octahedral complexes of the general composition [M(II)(BAMQH)₂]X₂ (where M = Cu(II), Ni(II), Co(II); X = Cl⁻, I⁻, ClO⁻₄ and BAMQH is biacetalmonoquinolylhydrazone); [M(II)(BAMQH)Cl₂.H₂O] (where M = Mn(II), Fe(III)) and penta-coordinated [VO(BAMQH)₂]SO₄ have been synthesized and characterized by magnetic susceptibility, optical and ESR studies in the polycrystalline and frozen states. [Ni(II)(BAMQH)₂]Cl₂ has tetrahedral geometry. Bidentate nature of the ligand is assumed in [Ni(II)(BAMQH)₂]Cl₂ and [VO(BAMQH)₂]SO₄ complexes.     

Crystal structure of (acetylacetonato) (dicarbonyl)iridium(I)

The structure of Ir(CO)₂(acac) is determined by XRD at room temperature. Crystallographic data for C₇H₇IrO₄ are: a = 6.4798(5) ?, b = 7.7288(5) ?, c = 9.1629(10) ?, α = 105.738(2)°, β = 90.467(3)°, γ = 100.658(2)°, space group 1, P , V= 433.24(6) ?³, Z = 2, d _calc = 2.662 g/cm³, R = 0.0167. The structure is built of isolated mononuclear molecules. The central iridium atom has a square coordination environment formed by two oxygen atoms that belong to the acetylacetonate ligand and two carbon atoms of carbonyl groups. The average Ir-O and Ir-C bond lengths are 2.045(3) ? and 1.832(6) ? respectively. Molecules are stacked in such a way that the planes of coordination squares turn out to be parallel to the Ir...Ir distances between the nearest neighbors in the stack of 3.242 ? and 3.260 ?. Original Russian Text Copyright ? 2009 by K. V. Zherikova, N. V. Kuratieva, and N. B. Morozova __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 3, pp. 595–597, May–June, 2009.     

Organic acid solutions in the chromatography of inorganic ions VIII. Cation-exchange of Mn(II), Cd(II), Co(II), Ni(II), Zn(II), Cu(II), Fe(III), Sc(III), Y(III), Eu(III), Dy(III), Ho(III), Yb(III), Ti(IV) and Nb(V) in malate media

Summary The cation-exchange behaviour of Mn(II), Cd(II), Co(II), Ni(II), Zn(II), Cu(II), Fe(III), Sc(III), Y(III), Eu(III), Dy(III), Ho(III), Yb(III), Ti(IV) and Nb(V) in malate media at various concentrations and pH, was studied with Dowex 50 WX8 resin (200–400 mesh) in the ammonium form. Separation of Fe(III)/Cu(II), Fe(III)/Cu(II)/Zn(II), Fe(III)/Co(II)/Mn(II), Cu(II)/Ni(II)/Mn(II), Fe(III)/Cu(II)/Co(II)/Mn(II), Fe(III)/Cu(II)/Ni(II)/Cd(II), Yb(III)/Eu(III), Sc(III)/Y(III),Sc(III)/Yb(III)/Dy(III) and Nb(V)/Yb(III)/Ho(III) has been achieved, among others.This work was supported by C.N.R. of Italy.     

Synthesis and Characterization of Bis(azido)bis(2‐chloropyridine)palladium(II), Bis(azido)bis(3‐chloropyridine)palladium(II), Bis(azido)bis(quinoline)palladium(II), and the Crystal Structure of Bis(azido)bis(quinoline)palladium(II)

Three new monomeric complexes of palladium(II) azide with 2‐chloropyridine ( 1 ), 3‐chloropyridine ( 2 ), and quinoline ( 3 ), have been synthesized by reaction of palladium nitrate and the respective Lewis‐base with sodium azide in a water/acetone mixture. All three compounds were characterized by IR, Raman, and multinuclear NMR spectroscopy. The composition of the complexes were confirmed by elemental analysis. The spectroscopic investigations confirm terminal azide ligands in trans position. Complex 3 was also characterized by crystallographic methods. Each palladium atom of 3 is surrounded in a distorted square planar fashion by 4 nitrogen atoms. The terminal azide ligands are in trans position.     

Complexes of dicamba with cadmium(II), copper(II), mercury(II), lead(II) and zinc(II)

New solid complexes of a herbicide known as dicamba (3,6-dichloro-2-methoxybenzoic acid) with Pb(II), Cd(II), Cu(II) and Hg(II) of the general formula M(dicamba)₂·xH₂O (M=metal, x=0-2) and Zn₂(OH)(dicamba)₃·2H₂O have been prepared and studied. The complexes have different crystal structures. The carboxylate groups in the lead, cadmium and copper complexes are bidentate, chelating, symmetrical, in Hg(dicamba)₂·2H₂O - unidentate, and in the zinc salt - bidentate, bridging, symmetrical. The anhydrous compounds decompose in three stages, except for the lead salt whose decomposition proceeds in four stages. The main gaseous decomposition products are CO₂, CH₃OH, HCl and H₂O. Trace amounts of compounds containing an aromatic ring were also detected. The final solid decomposition products are oxychlorides of metals and CuO. This revised version was published online in July 2006 with corrections to the Cover Date.     

One-step synthesis of core(Cr)/shell(gamma-Fe(2)O(3)) nanoparticles

Core(Cr)/shell(gamma-Fe(2)O(3)) nanoparticles were synthesized by mixing Fe(CO)(5) and Cr(CO)(6) in the 9:1 ratio. These particles exhibit narrow size distribution with 13.5 nm as mean diameter and uniform spherical shape. The TEM image, which is in good agreement with the synchrotron powder XRD pattern, reveals the heterogeneous nature (core/shell structure). The analysis of the pattern reveals gamma-Fe(2)O(3) structure and a metal crystal structure. Mossbauer spectra, which support the superparamagnetic behavior determined by H-M measurement, do not show any traceable amount of Fe(0). This suggests that the metal component is Cr. EELS analysis and iron mapping suggest controlled stoichiometry and also confirm a core made of Cr and a shell made of gamma-Fe(2)O(3).     

Synthesis of bis(diethyldithiocarbamato)manganese(II) and tris(diethyldithiocarbamato)manganese(III)

An ideal undergraduate introduction to the challenges of synthesis and characterization of air-sensitive compounds is accomplished in the preparation of bis(diethyldithiocarbamato)manganese(II). This economical experiment employs a glovebag, low-cost and low-toxicity chemicals, and is completed in one undergraduate laboratory period. For comparison purposes, the synthesis and characterization of air-stable tris(diethyldithiocarbamato)manganese(III) is also described.     

Polarographic analytical determination of Hg(II), Cu(II), Cd(II), As(III), Sb(III), Ti(IV) and U(VI) in the presence of Fe(III)

The analytical determination of Hg(II), Cu(II), Cd(II), As(III), Sb(III), Ti(IV) and U(VI) in the presence of Fe(III) and 1 M H₂SO₄ are investigated using the polarographic technique. The wave corresponding to the reduction of Fe(III) to Fe(II) was found to be completely suppressed by the addition of 1% pyrogallol. Thus, different mixtures of these elements, viz. Hg(II), Cu(II), Cd(II), As(III) and Fe(III)-mixture (A), Cu(II), Cd(II), Sb(III), As(III) and Fe(III)-mixture (B), and Cu(II), Cd(II), Ti(IV), U(VI) and Fe(III)-mixture (C), were quantitatively determined using 1% pyrogallol and 1 M H₂SO₄ as supporting electrolyte. The i₁/c results give excellent correlations in each case, as indicated from the results of leastsquares regression analysis.     

Fluorescence excitation spectra of the b (1)Pi(u), b(') (1)Sigma(u) (+), c(n) (1)Pi(u), and c(n) (') (1)Sigma(u) (+) states of N(2) in the 80-100 nm region

Fluorescence excitation spectra produced through photoexcitation of N(2) using synchrotron radiation in the spectral region between 80 and 100 nm have been studied. Two broadband detectors were employed to simultaneously monitor fluorescence in the 115-320 nm and 300-700 nm regions, respectively. The peaks in the vacuum ultraviolet fluorescence excitation spectra are found to correspond to excitation of absorption transitions from the ground electronic state to the b (1)Pi(u), b(') (1)Sigma(u) (+), c(n) (1)Pi(u) (with n=4-8), c(n) (') (1)Sigma(u) (+) (with n=5-9), and c(4) (')(v('))(1)Sigma(u) (+) (with v(')=0-8) states of N(2). The relative fluorescence production cross sections for the observed peaks are determined. No fluorescence has been produced through excitation of the most dominating absorption features of the b-X transition except for the (1,0), (5,0), (6,0), and (7,0) bands, in excellent agreement with recent lifetime measurements and theoretical calculations. Fluorescence peaks, which correlate with the long vibrational progressions of the c(4) (') (1)Sigma(u) (+) (with v(')=0-8) and the b(') (1)Sigma(u) (+) (with v(') up to 19), have been observed. The present results provide important information for further unraveling of complicated and intriguing interactions among the excited electronic states of N(2). Furthermore, solar photon excitation of N(2) leading to the production of c(4) (')(0) may provide useful data required for evaluating and analyzing dayglow models relevant to the interpretation of c(4) (')(0) in the atmospheres of Earth, Jupiter, Saturn, Titan, and Triton.     

Study of the Thermal Decompositions on N,N-Dialkyl-N'-Benzoylthiourea Complexes of Cu(II), Ni(II), Pd(II), Pt(II), Cd(II), Ru(III) and Fe(III)

The thermal decompositions of the complexes of N,N-dialkyl-N'-benzoylthioureas with Cu(II), Ni(II), Pd(II), Pt(II), Cd(II), Ru(III) and Fe(III) were studied by TG and DTA techniques. These metal complexes decompose in two stages: elimination of dialkylbenzamide, and total decomposition to metal sulphides or metals. The influence of the alkyl substituents in these benzoylthiourea chelates on the thermal behaviour of the metal complexes was investigated.This revised version was published online in November 2005 with corrections to the Cover Date.     

A crossed molecular beam study on the formation of hexenediynyl radicals (H(2)CCCCCCH; C(6)H(3) (X(2)A')) via reactions of tricarbon molecules, C(3)(X(1)Sigma(g)(+)), with allene (H(2)CCCH(2); X(1)A(1)) and methylacetylene (CH(3)CCH; X(1)A(1))

Crossed molecular beams experiments have been utilized to investigate the reaction dynamics between two closed shell species, i.e. the reactions of tricarbon molecules, C(3)(X(1)Sigma(g)(+)), with allene (H(2)CCCH(2); X(1)A(1)), and with methylacetylene (CH(3)CCH; X(1)A(1)). Our investigations indicated that both these reactions featured characteristic threshold energies of 40-50 kJ mol(-1). The reaction dynamics are indirect and suggested the reactions proceeded via an initial addition of the tricarbon molecule to the unsaturated hydrocarbon molecules forming initially cyclic reaction intermediates of the generic formula C(6)H(4). The cyclic intermediates isomerize to yield eventually the acyclic isomers CH(3)CCCCCH (methylacetylene reaction) and H(2)CCCCCCH(2) (allene reaction). Both structures decompose via atomic hydrogen elimination to form the 1-hexene-3,4-diynyl-2 radical (C(6)H(3); H(2)CCCCCCH). Future flame studies utilizing the Advanced Light Source should therefore investigate the existence of 1-hexene-3,4-diynyl-2 radicals in high temperature methylacetylene and allene flames. Since the corresponding C(3)H(3), C(4)H(3), and C(5)H(3) radicals have been identified via their ionization potentials in combustion flames, the existence of the C(6)H(3) isomer 1-hexene-3,4-diynyl-2 can be predicted as well.     

Methyl Tin(IV) derivatives of HOTeF(5) and HN(SO(2)CF(3))(2): a solution multinuclear NMR study and the X-ray crystal structures of (CH(3))(2)SnCl(OTeF(5)) and [(CH(3))(3)Sn(H(2)O)(2)][N(SO(2)CF(3))(2)

The new tin(IV) species (CH(3))(2)SnCl(OTeF(5)) was prepared via either the solvolysis of (CH(3))(3)SnCl in HOTeF(5) or the reaction of (CH(3))(3)SnCl with ClOTeF(5). It was characterized by NMR and vibrational spectroscopy, mass spectrometry, and single crystal X-ray diffraction. (CH(3))(2)SnCl(OTeF(5)) crystallizes in the monoclinic space group P2(1)/n (a = 5.8204(8) A, b =10.782(1) A, c =15.493(2) A, beta = 91.958(2) degrees, V = 971.7(2) A(3), Z = 4). NMR spectroscopy of (CH(3))(3)SnX, prepared from excess Sn(CH(3))(4) and HX (X = OTeF(5) or N(SO(2)CF(3))(2)), revealed a tetracoordinate tin environment using (CH(3))(3)SnX as a neat liquid or in dichloromethane-d(2) (CD(2)Cl(2)) solutions. In acetone-d(6) and acetonitrile-d(3) (CD(3)CN) solutions, the tin atom in (CH(3))(3)SnOTeF(5) was found to extend its coordination number to five by adding one solvent molecule. In the strong donor solvent DMSO, the Sn-OTeF(5) bond is broken and the (CH(3))(3)Sn(O=S(CH(3))(2))(2)(+) cation and the OTeF(5)(-) anion are formed. (CH(3))(3)SnOTeF(5) and (CH(3))(3)SnN(SO(2)CF(3))(2) react differently with water. While the Te-F bonds in the OTeF(5) group of (CH(3))(3)SnOTeF(5) undergo complete hydrolysis that results in the formation of [(CH(3))(3)Sn(H(2)O)(2)](2)SiF(6), (CH(3))(3)SnN(SO(2)CF(3))(2) forms the stable hydrate salt [(CH(3))(3)Sn(H(2)O)(2)][N(SO(2)CF(3))(2)]. This salt crystallizes in the monoclinic space group P2(1)/c (a = 7.3072(1) A, b =13.4649(2) A, c =16.821(2) A, beta = 98.705(1) degrees, V = 1636.00(3) A(3), Z = 4) and was also characterized by NMR and vibrational spectroscopy.     

Characterization and reactions of previously elusive 17-electron cations: electrochemical oxidations of (C(6)H(6))Cr(CO)(3) and (C(5)H(5))Co(CO)(2) in the presence of [B(C(6)F(5))(4)](-)

The electrochemical oxidations of (C6H6)Cr(CO)3, 1, and (C5H5)Co(CO)2, 2, when carried out in CH2Cl2/[NBu4][B(C6F5)4], allow the physical or chemical characterization of the 17-electron cations 1+ and 2+ at room temperature. The generation of 1+ on a synthetic time scale permits an electrochemical "switch" process involving facile substitution of CO by PPh3 as a route to (C6H6)Cr(CO)2PPh3. The radical 2+ undergoes a second-order reaction to give a product assigned as the metal-metal bonded dimer dication [Cp2Co2(CO)4]2+. The new anodic chemistry of these often-studied 18-electron compounds is made possible by increases in the solubility and thermal stability of the cation radicals in media containing the poorly nucleophilic anion [B(C6F5)4]-, TFAB.     

Organic acid solutions in the chromatography of inorganic ions. VII. Cation exchange of Mg(II), Ca(II), Sr(II), Ba(II), Mn(II), Cd(II), Co(II), Ni(II), Zn(II), Cu(II) and Fe(III) in succinate media

Summary The cation-exchange behaviour of Mg(II), Ca(II), Sr(II), Ba(II), Mn(II), Cd(II), Co(II), Ni(II), Zn(II), Cu(II) and Fe(III) in succinate media at various concentrations and pH, was studied with Dowex 50 WX8 resin (200–400 mesh) in the NH ₄ ⁺ form. As examples separations of Cd(II)/Co(II), Cd (II)/Ni(II), Fe(III)/Cu(II)/Ni(II) and Mg(II)/Ca(II)/Sr(II)/Ba(II) have been achieved.This work was supported by C.N.R. of Italy.     

Structural comparisons of silver(I) complexes of third-generation ligands built from tridentate (o-C(6)H(4)[CH(2)OCH(2)C(pz)(3)](2)) versus bidentate poly(1-pyrazolyl)methane units (o-C(6)H(4)[CH(2)OCH(2)CH(pz)(2)](2)) (pz = pyrazolyl ring)

The new bitopic, bis(1-pyrazolyl)methane-based ligand o-C6H4[CH2OCH2CH(pz)2]2 (L2, pz = pyrazolyl ring) is prepared from the reaction of (pz)2CHCH2OH (obtained from the reduction of (pz)2CHCOOH with BH3.S(CH3)2) with NaH, followed by the addition of alpha,alpha'-dibromo-o-xylene. The reaction of L2 with AgPF6 or AgO3SCF3 yields {o-C6H4[CH2OCH2CH(pz)2]2(AgPF6)}n or {o-C6H4[CH2OCH2CH(pz)2]2(AgO3SCF3)}n, respectively. Both compounds in the solid state have tetrahedral silver(I) centers arranged in a 1D coordination polymer network. The analogous ligand based on tris(1-pyrazolyl)methane units, o-C6H4[CH2OCH2C(pz)3]2 (L3), reacts with AgO3SCF3 to form a similar coordination polymer, {o-C6H4[CH2OCH2C(pz)3]2(AgO3SCF3)}n. In this case, each tris(pyrazolyl)methane unit in L3 adopts the kappa2-kappa0 bonding mode. Crystallization of a 3:1 mixture of AgO3SCF3 and L3 yields {o-C6H4[CH2OCH2C(pz)3]2(AgO3SCF3)2}n, in which the tris(1-pyrazolyl)methane units adopt a kappa2-kappa1 coordination mode.     

(Phosphine)gold(I) Complexes of Benzenedithioles. Crystal structures of 1,2-benzenedithiolato-bis[triphenyl-phosphinegold(I)] and bis(triethylphosphine)gold(I) bis(1,2-benzenedithiolato)gold(III)

The reaction of 1,2- and 1,3-benzenedithiol C₆H₄(SH)₂ with chloro(phosphine)gold(I) complexes R₃PAuCl (R = Et, Ph) in the presence of triethylamine in tetrahydrofuran gives stable gold(I) complexes 1,2-C₆H₄(SAuPR₃)₂ [R = Et ( 1 ) and Ph ( 2 )] or 1,3-C₆H₄(SAuPPh₃)₂ ( 3 ), respectively, in high yield. The compounds have been characterized by analytical and NMR spectroscopic data. From the reaction of 1,2-C₆H(SH)₂ with Et₃P? AuCl a by-product [(Et₃P)₂Au]⁺ [Au(1,2? C₆H₄S₂)₂]^? ( 4 ) has also been isolated in low yield. The crystal structures of compounds 2 and 4 have been determined by single crystal X-ray diffraction. The gold(I) atoms in complex 2 are two-coordinate with bond angles S? Au? P of 175.2(1) and 159.5(1)°, Au? S bond distances of 2.304(1) and 2.321(1) å, and a short Au…?Au contact of 3.145(1) Å. The gold(I) atom in the cation of complex 4 is also linearly two-coordinate with a P? Au? P angle of 170.1(1) Å and Au? P distances of 2.296(3) and 2.298(3) Å. The geometry of the anion in 4 shows a square-planar coordination of gold(III) by two chelating 1,2-benzenedithiolate ligands with Au? S distances between 2.299(3) and 2.312(3) Å (for two crystallographically independent, centrosymmetrical anions in the unit cell).