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.

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.

Conformation of a Fluorochrome from Aniline Blue

1997 ◽  
Vol 50 (10) ◽  
pp. 987
Author(s):  
Maureen F. Mackay, ◽  
Michael J. McTigue ◽  
Maruse Sadek
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Dimethyl Sulfoxide ◽  
Chemical Shifts ◽  
Deuterium Oxide ◽  
Sodium Ion ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
Solid State Conformation

The solid-state conformation of the fluorochrome sodium 4,4′-[carbonylbis(benzene-4,1-diyl)bis(imino)]-bisbenzenesulfonate has been defined by single-crystal X-ray crystallography. Monoclinic crystals belong to the space group C 2/c with a 11·732(1), b 6·185(1), c 37·179(3) Å, β 94·40(1)° and Z 8. The structure was refined to a final R0·042 for all 2271 unique terms. In the crystal six oxygen atoms form an octahedral grouping around the sodium ion and these octahedra are linked into layers sandwiched between the layers of organic anions which adopt an extended conformation. The n.m.r. spectra indicate that in solution the fluorochrome is flexible and averages to an extended structure that maintains symmetry about its longitudinal and carbonyl axes. Chemical shifts have been measured in water, deuterium oxide and (D6)dimethyl sulfoxide

Photochromic systems. Part 1. Structural and spectroscopic study of photochromically active products of Stobbe condensation. 2,3-Dibenzylidenesuccinic acid and its anhydride

1990 ◽  
Vol 68 (5) ◽  
pp. 741-746 ◽  
Author(s):  
P. Adriaan Davidse ◽  
Jan L. M. Dillen ◽  
Anton M. Heyns ◽  
Tomasz A. Modro ◽  
Petrus H. van Rooyen
Keyword(s):  
Cinnamic Acid ◽  
Structural Changes ◽  
Chemical Shifts ◽  
Spectroscopic Properties ◽  
Shielding Effect ◽  
Electron Charge ◽  
Hydrogen Atoms ◽  
Steric Strain ◽  
Space Group ◽  
Charge Densities

E,E-2,3-Dibenzylidenesuccinic acid (2) and its anhydride (1) were synthesized, their crystal structures and 1H and 13C nuclear magnetic resonance spectra were determined, and electron charge densities of carbon atoms were calculated. These results were related to the corresponding data available for E-cinnamic acid (3) in order to evaluate the effect of structural changes in a series 3 → 2 → 1 on the molecular parameters and spectroscopic properties of the cinnamic system. In the molecule of 2 most of the steric strain is released by the rotation about the C(α)—C(α′) bond giving rise to a structure consisting of two, approximately independent, cinnamic acid moieties. In 1, severe steric strain is introduced, as demonstrated by the unusually large values of the CCC bond angles exocyclic with respect to the anhydride ring, as well as by significant deviations from the plane of the cinnamic skeleton. The geometry of 1 results in an intramolecular shielding of the aromatic hydrogen atoms due to the proximity of the two benzene rings; this shielding effect for the ortho, meta, and para hydrogen atoms correlates well with the intramolecular distances between the corresponding positions of both rings. The common linear relationship between 13C chemical shifts and the electron charge densities on the given carbon atom has been obtained for compounds 1, 2, and 3.Crystal data. Anhydride (1): space group P21/c with a = 13.536(3), b = 14.391(3), c = 7.159(1) Å; β = 98.69(1)°; Rw = 0.029 and R = 0.055. Succinic acid (2): space group [Formula: see text] with a = 8.881(3), b = 9.786(1), c = 11.355(3) Å; α = 85.56(1), β = 88.76(2), γ = 69.46(2)°; Rw = 0.048 and R = 0.081. This compound cocrystallizes with one molecule of the solvent (acetic acid). Keywords: photochromic, cinnamic, succinic.

A Zigzag Chain Cd (II) Coordination Polymer Based on 2,4-Dinitro-benzoic Acid Ligand: Syntheses, Structure and Photoluminescence

2014 ◽  
Vol 997 ◽  
pp. 140-145
Author(s):  
Hui Bai ◽  
Hong Gao ◽  
Ming Hu
Keyword(s):  
Solid State ◽  
Coordination Polymer ◽  
Benzoic Acid ◽  
Room Temperature ◽  
Chain Structure ◽  
Zigzag Chain ◽  
Photoluminescent Property ◽  
X Ray ◽  
Acid Ligand ◽  
Carboxylate Groups

The coordination polymer, namely, [Cd (L)2(phen)]n (1) (HL=2,4-dinitro-benzoic acid, phen=1,10-phenanthroline) has been hydrothermally synthesized. Compound 1 was structurally characterized by IR spectra, thermogravimetric analysis and single-crystal X-ray diffractions. The carboxylate groups of L- adopt the bridging monodentate and bidentate modes to link two Cd2+ ions, resulting in a 1-D zigzag chain structure. The solid state photoluminescent property of 1 has been investigated at room temperature.

scholarly journals Titanocene Selenide Sulfides Revisited: Formation, Stabilities, and NMR Spectroscopic Properties

Molecules ◽  
2019 ◽  
Vol 24 (2) ◽  
pp. 319 ◽  
Author(s):  
Heli Laasonen ◽  
Johanna Ikäheimonen ◽  
Mikko Suomela ◽  
J. Mikko Rautiainen ◽  
Risto S. Laitinen
Keyword(s):  
13C Nmr ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
13C Nmr Spectroscopy ◽  
Spectroscopic Properties ◽  
Titanocene Dichloride ◽  
Enthalpies Of Formation ◽  
Spin Orbit Coupling ◽  
13C Nmr Spectra ◽  
Structure Determinations

[TiCp2S5] (phase A), [TiCp2Se5] (phase F), and five solid solutions of mixed titanocene selenide sulfides [TiCp2SexS5−x] (Cp = C5H5−) with the initial Se:S ranging from 1:4 to 4:1 (phases B–E) were prepared by reduction of elemental sulfur or selenium or their mixtures by lithium triethylhydridoborate in thf followed by the treatment with titanocene dichloride [TiCp2Cl2]. Their 77Se and 13C NMR spectra were recorded from the CS2 solution. The definite assignment of the 77Se NMR spectra was based on the PBE0/def2-TZVPP calculations of the 77Se chemical shifts and is supported by 13C NMR spectra of the samples. The following complexes in varying ratios were identified in the CS2 solutions of the phases B–E: [TiCp2Se5] (51), [TiCp2Se4S] (41), [TiCp2Se3S2] (31), [TiCp2SSe3S] (36), [TiCp2SSe2S2] (25), [TiCp2SSeS3] (12), and [TiCp2S5] (01). The disorder scheme in the chalcogen atom positions of the phases B–E observed upon crystal structure determinations is consistent with the spectral assignment. The enthalpies of formation calculated for all twenty [TiCp2SexS5−x] (x = 0–5) at DLPNO-CCSD(T)/CBS level including corrections for core-valence correlation and scalar relativistic, as well as spin-orbit coupling contributions indicated that within a given chemical composition, the isomers of most favourable enthalpy of formation were those, which were observed by 77Se and 13C NMR spectroscopy.

Intra- and inter-ion-pair protonic-hydridic bonding in polyhydridobis(phosphine)rhenates

2001 ◽  
Vol 79 (5-6) ◽  
pp. 964-976 ◽  
Author(s):  
Kamaluddin Abdur-Rashid ◽  
Alan J Lough ◽  
Robert H Morris
Keyword(s):  
Self Assembly ◽  
Electrostatic Interactions ◽  
Ion Pairs ◽  
Low Frequency ◽  
Chain Structure ◽  
Ion Pair ◽  
Proton Donor ◽  
Phosphine Ligands ◽  
Zigzag Chain ◽  
One Dimensional

The hexahydridobis(phosphine)rhenate anions, [ReH6(PR3)2]- (PR3 = PCy3, P-i-Pr3, PPh3, PMe3) were generated by potassium hydride deprotonation of the neutral heptahydride conjugate acids (ReH7(PR3)2), isolated as their [K(18-crown-6)]+ and [K(1,10-diaza-18-crown-6)]+ salts, and characterized by NMR and IR spectroscopy and elemental analyses. Structures from single crystal X-ray diffraction were obtained for the [K(1,10-diaza-18-crown-6)]+salts and these indicate the presence of short protonic—hydridic bonds involving the hydrides of the anions and the proton donor NH moieties of the cations. The structure of [K(1,10-diaza-18-crown-6)][ReH6(P-i-Pr3)2] adopts a one-dimensional zigzag chain with alternating cations and anions connected and held together by inter-ion N-H···Hx-Re interactions (x = 1 or 2). Short distances between the NH protons of the cations and hydrides of the anion ranging from 1.6 to 1.9 Å are estimated for this complex. A different kind of chain structure is observed for [K(1,10-diaza-18-crown-6)][ReH6(PMe3)2] in which the combined effects of inter-ion protonic—hydridic bonding (N-H···Hx-Re) and inter-ion electrostatic interactions (ReH-x···K+···H-xRe), result in one-dimensional networks of alternating cations and anions, with the metals and hydrides occupying the interior and the organic moieties of the phosphine ligands and crown ether lining the exterior of cylindrical supramolecular assemblies. A combination of intra- and inter-ion protonic-hydridic and intra-ion-pair electrostatic interactions in [K(1,10-diaza-18-crown-6)][ReH6(PPh3)2] result in the formation of discrete two-dimensional {[K(1,10-diaza-18-crown-6)][ReH6(PPh3)2]}4 tetramers. The PCy3 salt is disordered but appears to consist of isolated 1:1 ion pairs containing strong intra-ion-pair NH···HRe bonding. The solid-state IR spectra of the [K(1,10-diaza-18-crown-6)]+ salts show low-frequency shifts for the NH bands relative to [K(1,10-diaza-18-crown-6)][BPh4], and perturbed Re-H bands relative to those in the [K(18-crown-6)]+ salts. The magnitude of ΔνNH is related to the basicity of the anion as indicated by the pKαTHF of the conjugate acid form (ReH7(PR3)2), which increases as PPh3 < < PMe3 < P-i-Pr3 < PCy3. Solution 1H NMR, NOE, and T1 relaxation measurements of [K(1,10-diaza-18-crown-6)][ReH6(PPh3)2] indicate that these interactions also persist in toluene solutions of this compound.Key words: rhenium, hydride, phosphine, hydrogen bonding, self-assembly.

Syntheses and Crystal Structures of Silver(I) Organosulfur Polymers as One-Dimensional Chains

2003 ◽  
Vol 56 (11) ◽  
pp. 1167 ◽  
Author(s):  
Ruihu Wang ◽  
Maochun Hong ◽  
Weiping Su ◽  
Rong Cao ◽  
Yingjun Zhao ◽  
...  
Keyword(s):  
Self Assembly ◽  
Chain Structure ◽  
Zigzag Chain ◽  
X Ray Diffraction ◽  
Heterocyclic Ligands ◽  
Triclinic Space Group ◽  
Space Group ◽  
One Dimensional ◽  
Tetradentate Ligands ◽  
Quinoxaline Ring

Two silver(I) organosulfur coordination polymers, {[Ag2(mbpsq).dmf](NO3)2}n (1) and {[Ag3(bpsp)2(CH3CN)]-(BF4)3.2 H2O}n (2), were prepared by self-assembly of silver(I) with the chelating heterocyclic ligands mbpsq and bpsp (mbpsq = 2,3-bis[2-(4-methylpyrimidinyl)methylsulfanyl]-quinoxaline; bpsp = 2,6-bis[(2-pyrimidinyl)-methylsulfanyl]-pyridine). Single-crystal X-ray diffraction analysis reveals that (1) crystallizes in the triclinic space group P1– with a 10.1937(8), b 11.2160(9), c 13.8445(11) Å, α 103.0620(10), β 106.4850(10), γ; 96.2720(10)°, V 1452.8(2) Å3, Z 2. Each mbpsq molecule acts as a hexadentate ligand, in which two nitrogen atoms of the quinoxaline ring and adjacent sulfur atoms form two stable five-membered rings and two nitrogen atoms from different methylpyrimidine rings bridge two silver(I) centers to form a one-dimensional chain structure. Complex (2) crystallizes also in the triclinic space group P1– with a 12.8119(3), b 13.8902(4), c 15.4534(5) Å, α 70.6980(10), β 68.7570(10), γ; 85.3380(10)°, V 2416.83(12) Å3, Z 2. The bpsq molecules act as tridentate and tetradentate ligands ligating three silver(I) centres of different coordination environments to form a one-dimensional zigzag chain.

Structures and isomerization in diamminedichloropalladium(II)

1996 ◽  
Vol 52 (6) ◽  
pp. 909-916 ◽  
Author(s):  
S. D. Kirik ◽  
L. A. Solovyov ◽  
A. I. Blokhin ◽  
I. S. Yakimov ◽  
M. L. Blokhina
Keyword(s):  
Phase Transitions ◽  
Solid State ◽  
Powder Diffraction ◽  
Single Phase ◽  
Layer Structure ◽  
Powder Materials ◽  
Space Group ◽  
X Ray ◽  
Column Structure ◽  
Structure Determinations

Three forms (cis-, trans-, β-trans-) of [Pd(NH3)2Cl2] were obtained as pure single-phase powder materials. Ab initio structure determinations using X-ray powder diffraction were carried out. The cis-Pd(NH3)2Cl2 [a = 6.3121 (2), b = 6.4984 (2), c = 3.3886 (1) Å, α = 96.604 (4), β = 97.290 (4), γ = 104.691 (2)°, Z = 1, space group P1] and trans-Pd(NH3)2Cl2 [a = 6.5398 (3), b = 6.8571 (4), c = 6.3573 (3) Å, α = 103.311 (5), β = 102.454 (3), γ = 100.609 (4)°, Z = 2, space group P{\bar 1}] phases have a typical layer-column structure, while β-trans-Pd(NH3)2Cl2 [a = 8.1540 (2), b = 8.1482 (2), c = 7.7945 (1) Å, Z = 4, space group Pbca] is described as a parquet-like layer structure. Both trans phases demonstrate the order-disorder phenomenon. The possible ways of phase transitions are discussed. It is noted that the cis phase can transform into trans in the solid state without destroying the crystal body. Further transformation to β-trans follows through a break up of the crystal body.

scholarly journals Resolving Entangled JH-H-Coupling Patterns for Steroidal Structure Determinations by NMR Spectroscopy

Molecules ◽  
2021 ◽  
Vol 26 (9) ◽  
pp. 2643
Author(s):  
Danni Wu ◽  
Kathleen Joyce Carillo ◽  
Jiun-Jie Shie ◽  
Steve S.-F. Yu ◽  
Der-Lii M. Tzou
Keyword(s):  
Nmr Spectroscopy ◽  
1H Nmr Spectroscopy ◽  
Chemical Shifts ◽  
Atomic Level ◽  
Molecular Structures ◽  
Naturally Occurring ◽  
Structure Determinations ◽  
Ligand Interactions ◽  
Synthetic Steroids ◽  
The Individual

For decades, high-resolution 1H NMR spectroscopy has been routinely utilized to analyze both naturally occurring steroid hormones and synthetic steroids, which play important roles in regulating physiological functions in humans. Because the 1H signals are inevitably superimposed and entangled with various JH–H splitting patterns, such that the individual 1H chemical shift and associated JH–H coupling identities are hardly resolved. Given this, applications of thess information for elucidating steroidal molecular structures and steroid/ligand interactions at the atomic level were largely restricted. To overcome, we devoted to unraveling the entangled JH–H splitting patterns of two similar steroidal compounds having fully unsaturated protons, i.e., androstanolone and epiandrosterone (denoted as 1 and 2, respectively), in which only hydroxyl and ketone substituents attached to C3 and C17 were interchanged. Here we demonstrated that the JH–H values deduced from 1 and 2 are universal and applicable to other steroids, such as testosterone, 3β, 21-dihydroxygregna-5-en-20-one, prednisolone, and estradiol. On the other hand, the 1H chemical shifts may deviate substantially from sample to sample. In this communication, we propose a simple but novel scheme for resolving the complicate JH–H splitting patterns and 1H chemical shifts, aiming for steroidal structure determinations.

Zum Mineral Johillerit verwandte Oxovanadate RbCd4V3O12 und TlCd4V3O12 / Oxovanadates RbCd4V3O12 and TlCd4V3 O12 Related to the Mineral Johillerite

1997 ◽  
Vol 52 (5) ◽  
pp. 663-668 ◽  
Author(s):  
B. Mertens ◽  
Hk. Müller-Buschbaum
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Single Crystals ◽  
Solid State Reactions ◽  
Space Group ◽  
Related Compounds

Abstract Single crystals of I RbCd4V3O12 and TlCd4V3O12 II have been prepared by solid state reactions in closed iron tubes. The compounds crystallize closely related to the Johillerite structure in the space group C62h- C2/c with I: a = 13.058(3); b - 13.528(3), c = 7 .0 6 0 (2 )Å , β = 114.88(2)°; II: a = 12.999(6), b = 13.527(7), c = 7.055(3) Å , β = 114.88(4)°, Z = 4. Special features are the loss of Cu2+ in order to gain an additional Cd2+ position. The crystal structure is discussed with respect to related compounds of the Johillerite type.

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