Synthesis, Structures and Spectroscopic Properties of 1 : 1 Complexes of Gold(I) Halides with Trimesitylphosphine

2000 ◽  
Vol 53 (3) ◽  
pp. 175 ◽  
Author(s):  
Raymond C. Bott ◽  
Graham A. Bowmaker ◽  
Robbie W. Buckley ◽  
Peter C. Healy ◽  
M. C. Senake Perera
Keyword(s):  
Infrared Spectroscopy ◽  
Solid State ◽  
Far Infrared ◽  
Spectroscopic Properties ◽  
Far Infrared Spectroscopy ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Structure Determinations ◽  
Far Infrared Spectra

Monomeric two-coordinate gold(I) complexes, [Au(P(mes)3)X] (P(mes)3 = tris(2,4,6-trimethylphenyl)phosphine, X = Cl, Br and I), have been prepared and characterized by single-crystal X-ray structure determinations, far-infrared spectroscopy and solution and solid-state CPMAS 31 P n.m.r. spectroscopy. X-Ray structure determinations show that crystals obtained from solutions of [NBu4] [AuX2] and P(mes)3 in acetonitrile for X = Cl, Br and I and in dimethylformamide (dmf) for X = Br and I form an isomorphous series of complexes, crystallizing in space group P21/c with a ª 8, b ª 22, c ª 13 Å, b ª 98˚ (a form). Crystallization of the chloride from dimethylformamide yields the solvated complex [Au(P(mes)3)X]·(dmf) in space group P2/a with a 15.224(2), b 10.070(1), c 18.210(4) Å, b 100.42(2)˚. Electrochemical synthesis of the complexes for X = Cl and Br yield two new crystalline phases; the chloride in space group P21/c with a 10.249(2), b 8.189(2), c 31.844(3) Å, b 91.68(1)˚ (b form) and the bromide in space group Pbca with a 19.208(4), b 15.586(3), c 16.962(4) Å ( g form). The Au–P bond lengths increase in the order Cl < Br < I with distances c. 0.02–0.03 Å longer than average values for other [Au(PR3)X] complexes, reflecting steric congestion by the P(mes)3 ligand. For the unsolvated complexes, the Au–X distances are c. 0.02 Å shorter than average values. For the Cl/dmf solvate, both Au–P and Au–X bond lengths increase. For the a complexes, far-infrared spectra show n(Au 35,37 Cl) 336, 329 cm –1 , n(AuBr) 234 cm –1 and n(AuI) 195 cm –1 and solid-state 31 P CPMAS n.m.r. spectra yield broad peaks with d–3.9 (Cl), –0.6 (Br) and +6.0 I). For the Cl/dmf solvate, n(Au 35,37 Cl) are 334, 327 cm –1 and d is –4.4. Solution 31 P n.m.r. spectra in CDCl3 give sharp single peaks at d –5.0 (Cl), –1.4 (Br) and +5.5 (I) with the similarity of the values with those for the solid-state spectra consistent with similar conformational structures for the [Au(P(mes)3)X] molecules in the two states.

Synthesis, Structures and Spectroscopic Properties of 1 : 1 Complexes of Gold(I) Halides with Tricyclohexylphosphine, [Au(PCy3)X], X = Cl, Br and I

1999 ◽  
Vol 52 (4) ◽  
pp. 271 ◽  
Author(s):  
Raymond C. Bott ◽  
Graham A. Bowmaker ◽  
Robbie W. Buckley ◽  
Peter C. Healy ◽  
M. C. Senake Perera
Keyword(s):  
Solid State ◽  
Chemical Shifts ◽  
Far Infrared ◽  
Spectroscopic Properties ◽  
Chain Structure ◽  
Phosphine Ligands ◽  
Zigzag Chain ◽  
Conformational Structure ◽  
Space Group ◽  
Structure Determinations

Two-coordinate gold(I) complexes, [Au(PCy3)X] (PCy3 = tricyclohexylphosphine, X = Cl, Br and I), have been prepared by reaction of stoichiometric quantities of [NBu4] [AuX2] and PCy3 in dimethylformamide and, for X = Cl and Br, by anodic dissolution of metallic gold in a solution of aqueous HX and PCy3 in acetonitrile. The complexes were characterized by solution and solid-state 31 P n.m.r. spectroscopy, far-infrared spectroscopy and single-crystal X-ray structure determinations. The chloride, bromide and iodide complexes form an isomorphous series, crystallizing in the triclinic space group P 1- (a ≈ 9·3, b ≈ 10·3, c ≈ 10·9 Å, α ≈ 88, β ≈ 80, γ ≈ 77°) as discrete molecules which stack in parallel head-to-tail mode to form a zigzag chain of gold atoms along the crystallographic c axis. Au ··· Au separations are 5·71, 6·20 Å for X = Cl, 5·72, 6·17 Å for X = Br and 5·74, 6·20 Å for X = I. The iodide also crystallizes as an orthorhombic form in space group Pnma (a 16·809(4), b 14·373(5), c 8·623(3) Å) with a different conformational structure for the PCy3 ligand and loss of the zigzag chain structure. Far-infrared spectra of the complexes show ν(AuX) at 332, 324 cm-1 for X = Cl and 232 cm-1 for X = Br with multiple bands in the region 150−200 cm-1 for both iodide complexes, precluding definitive assignment of ν(AuI). Solution 31 P n.m.r. spectra in chloroform give sharp single peaks with chemical shifts of 54·5, 56·6 and 59·9 ppm for X = Cl, Br and I respectively. The solid-state CPMAS 31 P n.m.r. spectra also yield single peaks with chemical shifts of 55 (Cl), 58 (Br) and 63 ppm (I) for the triclinic complexes and 57 ppm for the orthorhombic iodide. The chemical shift differences between the two forms of the iodide and between the complexes in the solution and solid states are ascribed to variations in the conformational structure of the phosphine ligands.

Tetraalkylammonium Bromochlorocuprates(II)

1979 ◽  
Vol 32 (3) ◽  
pp. 691 ◽  
Author(s):  
DW Smith ◽  
T Yeoh
Keyword(s):  
Infrared Spectroscopy ◽  
Powder Diffraction ◽  
Far Infrared ◽  
Far Infrared Spectroscopy ◽  
X Ray

(NMe4)2CuBrnC14-n and (NEt4)nCuBrnCl44-n (n = 1, 2, 3) have been prepared and characterized by X-ray powder diffraction and far-infrared spectroscopy. The tetramethylammonium compounds are isomorphous with each other and with the corresponding compounds where n = 0, 4. The tetraethylammonium compounds constitute another isomorphous series. All the compounds apparently contain discrete CuBrnCI4-n2- anions, with flattened tetrahedral configurations.

Synthesen und Kristallstrukturen von [PPh3Me]NO2 und [PPh3 Me]HCO2H2O / Syntheses and Crystal Structures of [PPh3Me]NO2 and [PPh3Me]HCO2H2O

1988 ◽  
Vol 43 (10) ◽  
pp. 1279-1284 ◽  
Author(s):  
Mervat El Essawi ◽  
H Gosmann ◽  
D Fenske ◽  
F Schmock ◽  
K Dehnicke
Keyword(s):  
Crystal Structure ◽  
Aqueous Solutions ◽  
Ir Spectra ◽  
Bond Angle ◽  
Water Molecules ◽  
Moist Air ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Structure Determinations

Triphenylmethylphosphonium nitrite and formate have been prepared by the reaction of [PPh3Me]I with silver nitrite, and lead formate, respectively, in aqueous solutions. [PPh3Me]NO2 (1) forms pale yellow crystals, and [PPh3Me]HCO2·H2O (2) forms white crystals. Both compounds are soluble in water, ethanol, and dichloromethane. In moist air 2 is hydrated to yield [PPh3Me]HCO2·2H2O (3). The compounds were characterized by their IR spectra, 1 and 2 also by X-ray crystal structure determinations.[PPh3Me]NO2 (1): space group P21/n, Z = 4, 2088 independent observed reflexions, R = 0.062. Lattice dimensions (20 °C): a = 914.7(3), b = 1887.5(9), c = 1080.0(4) pm, β = 110.29(3)°. The compound consists of PPh3Me+ ions and NO2- anions with bond lengths of 114.2(6) pm and a bond angle of 124.1(7)°. [PPh3Me]HCO2·H2O (2): space group P21/n, Z = 4, 2973 independent observed reflexions, R = 0.069. Lattice dimensions (-20 °C): a = 931(2), b = 1558(3), c = 1281(2) pm, β = 105.9(1)°. The compound consists of PPh3Me+ ions and formate anions which form centrosymmetric dimeric units [HCO2·H2O]22- through hydrogen bridges of the water molecules. Bond lengths CO 122.4(4) and 120.9(4) pm. bond angle OCO 129.9(4)°.

Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXIV Syntheses, Spectroscopy and Structures of Some 1 : 4 Adducts of Copper(I) and Silver(I) Perchlorates with Triphenylarsine and Triphenylstibine

1997 ◽  
Vol 50 (6) ◽  
pp. 539 ◽  
Author(s):  
Graham A. Bowmaker ◽  
Effendy ◽  
Robert D. Hart ◽  
John D. Kildea ◽  
Brian W. Skelton ◽  
...  
Keyword(s):  
Room Temperature ◽  
Far Infrared ◽  
Lewis Base ◽  
X Ray ◽  
Cation Disorder ◽  
Structure Determinations ◽  
Consistent Picture ◽  
Far Infrared Spectra

Syntheses and room-temperature single crystal X-ray structure determinations are recorded for adducts [M(EPh3)4] (ClO4), M = Cu, E = As (1), Sb (2); M = Ag, E = As (3), Sb (4), enabling comparison with analogous, previously studied MP4 and MN4 environments. The four complexes so characterized all crystallize in the familiar rhombohedral R-3 array (a ≈ 14·4, c ≈ 52 Å, hexagonal setting) with the metal and chlorine atoms located on crystallographic threefold axes. In these arrays Cu–E (axial, off axis) are 2·493(2), 2·533(1) for (1), and 2·572(1), 2·577(1) Å for (2), the disparity in the two independent M-E distances being diminished relative to those of previously studied phosphorus analogues, perhaps in consequence of increasing E size. In (3) and (4), some cation disorder is evident in respect of the ligand pnictide atom (E); for the major components Ag-E are 2·652(3), 2·680(2) in (3); 2·732(2), 2·7295(8) Å in (4). Problems associated in defining the metal atom environment geometries in the latter are, nevertheless, more satisfactorily overcome in two further determinations of nitrate salts: [Ag(SbPh3)4] (NO3) (5) is of the rhombohedral family with no cation core disorder, Ag–E (axial, off axis) being 2·720(4), 2·725(2) Å, while the structural characterization of a 1 : 4 triphenylarsine adduct of silver nitrate is recorded as its tetraethanol solvate, namely [Ag(AsPh3)4] (NO3).~ 4C2H5OH(6), monoclinic, C2/c, a 18·373(4), b 20·786(5), c 21·070(8) Å, β 108·18(3)°, Z = 4 f.u. The silver atom of the [Ag(AsPh3)4]+cation unusually lies on a crystallographic 2 (rather than a 3 ) axis of the incipiently23 (T) array, with Ag-As 2·649(2), 2·650(2) Å and As-Ag-As ranging from 108·22(4) to 111·41(6)°. The structure determination of a chloroform solvate of (2), denoted (2a), of low precision, is noted, together with the structure of an interesting artefact, isomorphous with the rhombohedral oxoanion array, modelled as [Ag(PPh3)4]2 (SiF6).py (7). Bands in the far-infrared spectra of [M(AsPh3)4] (ClO4) are assigned to v(MAs) vibrations at 119 (M = Cu) and 103 cm¯1 (M = Ag); this produces a more consistent picture of the variation in the wavenumbers of the v(ME) modes in [M(EPh3)4]+ compounds than was available previously.

6 MeV storage ring dedicated to hard X-ray imaging and far-infrared spectroscopy

Pramana ◽  
2011 ◽  
Vol 76 (2) ◽  
pp. 351-355
Author(s):  
M M HAQUE ◽  
A MOON ◽  
T HIRAI ◽  
H YAMADA
Keyword(s):  
Infrared Spectroscopy ◽  
Storage Ring ◽  
Far Infrared ◽  
Far Infrared Spectroscopy ◽  
X Ray ◽  
X Ray Imaging

Fourier transform far-infrared spectroscopy of HN2+ on the AILES beamline of synchrotron SOLEIL

2013 ◽  
Vol 91 (11) ◽  
pp. 937-940 ◽  
Author(s):  
S. Gruet ◽  
A. Morvan ◽  
O. Pirali ◽  
T. Chamaillé ◽  
E. Bouisset ◽  
...  
Keyword(s):  
Fourier Transform ◽  
Infrared Spectroscopy ◽  
Broad Band ◽  
Far Infrared ◽  
Far Infrared Spectroscopy ◽  
Pure Rotation ◽  
Frequency Tunable ◽  
Discharge Cell ◽  
Rotation Spectrum ◽  
Far Infrared Spectra

We report the pure rotation spectrum of HN2+ as measured by Fourier transform (FT) absorption spectroscopy in the 20–40 cm−1 spectral range. The cations are produced in a liquid nitrogen cooled hollow cathode discharge cell developed on the AILES beamline of synchrotron SOLEIL. The setup was optimized by recording rotation–vibration spectra of H3+ (with the ν2 band centered at about 2521 cm−1), HN2+ (with the ν1 band centered at about 3234 cm−1), and HCO+ (with the ν1 band centered at about 3089 cm−1). Many rotation–vibration lines have been assigned for each ion and five pure rotational transitions have been detected for HN2+. These results demonstrate the feasibility of recording far-infrared spectra of cationic species using FT broad band spectroscopy associated with the bright synchrotron radiation continuum as an alternative to laser-based frequency tunable techniques.

Isoselenocyanatoborate -Kristallstrukturen von (n-Bu4N)[BH(NCSe)3] und (Ph4P)[B3H7(NCSe)] / Isoselenocyanatoborates -Crystal Structures of (n-Bu4N)[BH(NCSe)3] and (Ph4P)[B3H7(NCSe)]

1998 ◽  
Vol 53 (3) ◽  
pp. 271-274 ◽  
Author(s):  
B. Steuer ◽  
W. Preetz
Keyword(s):  
Single Crystals ◽  
Crystal Structures ◽  
Elemental Selenium ◽  
Monoclinic Space Group ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Structure Determinations ◽  
Average Bond

Abstract The treatment of [B6H6]2- with an excess of (SCN)2 in dichloromethane in the presence of solid KOH gives the hexaisoselenocyanatodiborate anion [B2(NCSe)6]2- as an intermediate (δ(11B) = -10.3 ppm), from which [BH(NCSe)3]- and elemental selenium are formed. The X-ray structure determinations on single crystals of (n-Bu4N)2[BH(NCSe)3] (1) (triclinic, space group Pi with a = 8.512(2), b = 10.885(3), c = 14.895(4) Å, α = 79.52(2), β = 74.86(2), γ = 86.768(2)°, Z = 2) and (Ph4P)[B3H7(NCSe)] (2) (monoclinic, space group C2, a = 7.686(5), b = 10.366(3), c = 17.533(3) A, β = 108.89°, Z = 4) show that the selenocyanate groups are coordinated exclusively via the N atoms with average bond lengths of B-N = 1.52, C-N = 1.15, C-Se = 1.75 A and angles N-C-Se = 179°, B-N-C = 168.7 - 176.8°. The N-B-N angles of 1 range from 107.5 to 109.5°.

Vibrational spectra of adducts of iodine monochloride with some pyridine bases

1980 ◽  
Vol 33 (8) ◽  
pp. 1743 ◽  
Author(s):  
GA Bowmaker ◽  
K Tan ◽  
MJ Taylor
Keyword(s):  
Infrared Spectroscopy ◽  
Solid State ◽  
Far Infrared ◽  
Pyridine Derivative ◽  
Iodine Monochloride ◽  
Far Infrared Spectroscopy ◽  
Model Yield ◽  
Pyridine Bases ◽  
Yield Information ◽  
Structure And Bonding

A series of molecular adducts, L-ICl, where L = pyridine or a pyridine derivative, have been prepared and the solid state spectra examined by Raman and far-infrared spectroscopy. Assignments of the modes v(I-Cl) 240-300 cm-1 and v(N-I) 90-180 cm-1 and force constant calculations on a simple three-centre model yield information on structure and bonding related to the nature of the pyridine donor. Several ionic products containing the Icl2- ion have been encountered.

Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXX Synthesis, Spectroscopy and Structural Systematics of 1 : 2 Binuclear Adducts of Copper(I) Halides with Triphenylstibine, [(Ph3Sb)2Cu(-X)2Cu(SbPh3)2], X = Cl, Br, I

1997 ◽  
Vol 50 (6) ◽  
pp. 621 ◽  
Author(s):  
Robert D. Hart ◽  
Graham A. Bowmaker ◽  
Eban N. de Silva ◽  
Brian W. Skelton ◽  
Allan H. White
Keyword(s):  
Single Crystal ◽  
Infrared Spectra ◽  
Related Species ◽  
Far Infrared ◽  
Lewis Base ◽  
The Other ◽  
X Ray ◽  
Structure Determinations ◽  
Far Infrared Spectra

Crystallization of 1 : 2 mixtures of the copper(I) halides CuX, X = Cl, Br, I, with triphenylstibine from acetonitrile yields adducts of 1 : 2 CuX/SbPh3 stoichiometry, confirmed by single-crystal X-ray structure determinations. The three complexes are isomorphous, monoclinic, P 21/c, a ≈ 24·3, b ≈ 14·2, c ≈ 20 Å, β 110°, Z = 4 dimers; conventional R on F were 0·047, 0·044 and 0·045 for No 11247, 4673 and 10418 independent ‘observe’ (I > 3σ(I)) reflections respectively. The complexes, also isomorphous with some related species, e.g. 1 : 2 AgBr,I/AsPh3, are dimers: [(Ph3Sb)2Cu(µ-X)2Cu(SbPh3)2]. The chloride is also recorded as a chloroform disolvate, isomorphous with its arsine analogue, being monoclinic, C 2/c, a 21·486(9), b 17· 925(9), c 19·972(7) Å, β 91·31(3)°, Z = 4 dimers, R 0·057 for No 3756. The far-infrared spectra of [(Ph3Sb)2Cu(µ-X)2Cu(SbPh3)2] (X = Br, I) showed no clear v(CuX) bands, in contrast to the situation reported previously for the corresponding Ph3As compounds. A possible v(CuCl) band is observed in the X = Cl complex at 219 cm-1 , but this occurs in a region where there is also significant absorption in the other two compounds. The absence of strong v(CuX) bands in these complexes is consistent with the situation observed previously for the 3 : 1 compounds [(Ph3Sb)3CuX].

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