Thiophenophane–metal complexes. I. Preparation, X-ray structure, and cyclic voltammetry of 2,5,8-trithia[9](2,5)thiophenophane, L, and of its metalcomplexcation bis(2,5,8-trithia[9](2,5)thiophenophane-S2,S3]copper(I),[CuL2]+1

1988 ◽  
Vol 66 (6) ◽  
pp. 1506-1512 ◽  
Author(s):  
C. Robert Lucas ◽  
Liu Shuang ◽  
Michael J. Newlands ◽  
Jean-Pierre Charland ◽  
Eric J. Gabe
Keyword(s):  
Cyclic Voltammetry ◽  
Reference Electrode ◽  
Molecular Structures ◽  
Saturated Calomel Reference Electrode ◽  
Coordination Geometry ◽  
Tetrahedral Coordination ◽  
Space Group ◽  
X Ray ◽  
H Nmr ◽  
Distorted Tetrahedral Coordination

Preparation of the thiophenophane C10H14S4, (L), and syntheses of its copper(I) complex [CuL2]ClO4 or [CuL2]BF4 are described. The 13C and 1H nmr spectra of L and the ir spectra (4000–200 cm−1) of [CuL2]ClO4 and [CuL2]BF4 are reported. The molecular structures of L and [CuL2]ClO4 have been determined. For L: space group P21/a, a = 7.9347(2) Å, b = 18.7479(3) Å, c = 8.8596(2) Å, β = 108.446(2)°, Z = 4, Rf = 0.048, and Rw = 0.034. For [CuL2]ClO4: space group P21/c, a = 9.4363(1) Å, b = 18.2768(3) Å, c = 16.2157(3) Å, β = 96.520(2)°, Z = 4, Rf = 0.056, and Rw = 0.037. The Cu(I) complex has distorted tetrahedral coordination geometry; its perchlorate anion is non-coordinating and disordered. The Cu—S bond lengths lie in the range 2.301–2.392 Å and the S—Cu—S angles in the range 92.43—150.26°. Cyclic voltammetry of [CuL2]ClO4 (10−3 mol/L in dimethylsulfoxide, 0.1 mol/L Et4NClO4, glassy carbon working electrode, platinum counter electrode, aqueous saturated calomel reference electrode against which the ferrocenium/ferrocene potential under similar conditions was 400 mV) shows a quasi-reversible oxidation (E1/2 = 0.150 V, ΔEp = 170 mV at 50 mV/s). Thiophene's effect as a sub-unit in a small macrocycle upon properties of the latter is discussed.

Spectroscopic and X-Ray Investigation of Cobalt(III) Complexes with 2-Oximinocarboxylic Acids

1993 ◽  
Vol 48 (4) ◽  
pp. 409-417 ◽  
Author(s):  
Rostislav D. Lampeka ◽  
Zamira D. Uzakbergenova ◽  
Victor V. Skopenko
Keyword(s):  
Electronic Absorption Spectra ◽  
Molecular Structures ◽  
X Ray Diffraction ◽  
Octahedral Structure ◽  
Space Group ◽  
X Ray ◽  
H Nmr ◽  
Nmr Data ◽  
R Factors

Mixed complexes of Co(III) with 2-oximinopropionic (H2A) or 2-oximino-3-phenylpropionic (H2B) acid and different amine (imidazole, benzimidazole, pyridine, β-picoline, γ-picoline) are reported. Characterization of the complexes was based upon elemental analysis, conductivity and JR, 1H NMR, and electronic absorption spectra, and X-ray diffraction analysis. The organic ligands behave as O,N donors via the carboxyl oxygen and the oxime nitrogen atoms. A trans-octahedral structure has been assigned to the bis(2-oximinocarboxylato)bis(amine)cobalt(III) on the basis of 1H NMR data.The crystal and molecular structures of the complexes trans-[bis(2-oximinopropionato)bis-(imidazole)]- (I) and trans-[bis(2-oximinopropionato)bis(pyridine)]cobalt(III) (II) were determined. I crystallizes in space group P2/n with a = 14.1 67(2), b = 8.774(1), c = 14.785(2) Å,β = 113.37(1)°, Z = 4, Dcalc = 1.568 g · cm-3. II crystallizes in space group P1̄ with a = 9.122(2), b = 10.038(2), c = 11.759(2) Å, α = 69.95(1)°, β = 67.47(2)°, γ = 69.49(2)°, Ζ = 2, Dcalc = 1.547 g cm-3. The structures were refined to unweighted R factors of 0.036 and 0.028, respectively. The coordination sphere around Co is pseudo-octahedral with the 2-oximinopropionato ligands occupying four equatorial positions, and the amines in axial positions.

Anionic pyrazolyl-bridged nickel nitrosyl complexes. Synthesis, structure, and reactivity

1979 ◽  
Vol 57 (23) ◽  
pp. 3099-3106 ◽  
Author(s):  
Kenneth S. Chong ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Ion Pair ◽  
Sodium Ion ◽  
Coordination Geometry ◽  
Tetrahedral Coordination ◽  
Space Group ◽  
Nitrosyl Complexes ◽  
Pyrazolyl Group ◽  
The Mean ◽  
Distorted Tetrahedral Coordination ◽  
Molecular Unit

A series of anionic pyrazolyl-bridged nickel nitrosyl complexes, M+[(ON)Ni(μ-L2)(μ-X)Ni(NO)]− (where L = pyrazolyl, N2C3H3, or 3,5-dimethylpyrazolyl, N2C5H7; X = Cl, Br, I, or N2C5H7; and M = Na, (CH3)4N, or (C2H5)4N) is described. Crystallographic analyses have been carried out on two of these complexes. Crystals of [(C2H5)4N]+[(ON)Ni(μ-I)(μ- N2C5H7)2Ni(NO)]− are orthorhombic, a = 19.910(1), b = 14.0330(7), c = 9.3195(9) Å, Z = 4, space group Pn21a and crystals of [(C4H8O)2Na][(ON)Ni(μ-N2C5 H7)3Ni(NO)] are orthorhombic, a = 19.897(2), b = 19.529(3), c = 15.894(2) Å, Z = 8, space group Pbca. Both structures were solved by Patterson and Fourier syntheses and were refined by full-matrix least-squares procedures to R = 0.027 and 0.057 for 2572 and 2168 reflections with I ≥ 3σ(I) respectively. The structure of [(C2H5)4N]+[(ON)Ni(μ-I)(μ-N2C5H7)2Ni(NO)]− consists of discrete cations and binuclear anions which have approximate C2v symmetry. The nickel atoms have distorted tetrahedral coordination geometry. Important mean molecular dimensions (distances corrected for libration) are: Ni—I—Ni, 73.67(2)°, Ni—I, 2.765(3), Ni—NO, 1.649(5), Ni—N(pyrazolyl), 1.980(14) Å, and Ni—N—O, 172.5(18)°. The structure of [(C4H8O)2Na][(ON)Ni(μ-N2C5 H7)3Ni(NO)] consists of discrete ion-pair units in which the two NiNO moieties are bridged by three N2C5H7 ligands, two of which are coordinated to the sodium ion via a novel η2(N,N) π-interaction (mean Na—N = 2.61(3) Å). The sodium is also coordinated to two tetrahydrofuran oxygen atoms to give a distorted tetrahedral coordination geometry about the sodium (Na—O = 2.301(6) and 2.266(5) Å). Except for disordered tetrahydrofuran carbon atoms, the molecular unit has approximate C2v symmetry. The nickel atoms have distorted tetrahedral coordination geometry, the mean distances being Ni—NO, 1.591(6), Ni—N(pyrazolyl), 1.985(2) for the unique pyrazolyl group and 2.016(5) Å for the pyrazolyl nitrogen atoms coordinated to Na. The mean Ni—N—O angle is 176.9(11)°.

scholarly journals Synthesis and Characterisation of Zinc(II) Complex With 2-Amino-5-bromopyridine Ligand

2017 ◽  
Author(s):  
Fitriani
Keyword(s):  
Ir Spectroscopy ◽  
Elemental Analysis ◽  
Coordination Geometry ◽  
Tetrahedral Coordination ◽  
Visible Absorption ◽  
X Ray ◽  
X Ray Crystallography ◽  
Uv Visible ◽  
Cl Atoms ◽  
Distorted Tetrahedral Coordination

The synthesis and characterisation of zinc(II) complex with 2-amino-5-bromopyridine (C5H5BrN2) ligand have been described. The complex was structurally characterised via X-ray crystallography, in the title compound, (2-amino-5-bromopyridinium) [ZnCl¬3(2-amino-5-bromopyridine)] or which is also called (C5H6BrN2) [ZnCl3(C5H5BrN2)]¬. The Zn(II) atom is four-coordinated by three Cl atoms and one imine N-atom of 2-amino-5-bromopyridine ligand, forming a distorted tetrahedral coordination geometry. The complex was also investigated by elemental analysis, 1H NMR, IR spectroscopy and UV-Visible absorption. The protonation behaviour upon coordination is discussed.

Synthesis, characterization, and X-ray structural analysis of the Cu(I) derivative, [Me2Ga(OCH2CH2NMe2)N2C5H7]Cu• PPh3

1981 ◽  
Vol 59 (3) ◽  
pp. 518-523 ◽  
Author(s):  
Kenneth S. Chong ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Structural Analysis ◽  
Copper Atom ◽  
Direct Methods ◽  
Carbonyl Complex ◽  
Coordination Geometry ◽  
Tetrahedral Coordination ◽  
Full Matrix ◽  
X Ray ◽  
Complex Crystals ◽  
Distorted Tetrahedral Coordination

The Cu(I) complex [Me2Ga(OCH2CH2NMe2)N2C5H7]Cu•PPh3 has been synthesized and its fluxional behavior in solution probed. Attempts have been made to isolate the analogous Cu(I) carbonyl complex. Crystals of [dimethyl(3,5-dimethyl-1-pyrazolyl)(N,N-dimethylethanolamino)gallato (N(2),O,N(3))](triphenylphosphine)copper(I) are monoclinic, a = 18.871(2), b = 9.464(1), c = 18.374(2) Ā, β = 109.62(1)°, Z = 4, space group P21/c. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.028 and Rw = 0.035 for 2729 reflections with I ≥ 3σ(I). The copper atom is bonded to the phosphine and to the tridentate Me2Ga(OCH2CH2NMe2)N2C5H7− ligand resulting in a distorted tetrahedral coordination geometry. The Cu—P distance of 2.156(1) Å is unusually short. Other important bond distances (corrected for libration) are: Cu—O, 2.163(2), Cu—N(pyrazolyl), 2.025(3), Cu—N(amino), 2.144(3), Ga—O, 1.896(3), Ga—N, 2.005(3), and Ga—C, 1.972(5) and 1.987(5) Å.

Reaktionen des (2-TrimethylsiIoxyphenyl)diphenylphosphans mit Phosphorhalogeniden – Kristall- und Molekiilstruktur des (2-Hydroxyphenyl)diphenylphosphoniumbromids / Reactions of (2-Trimethylsiloxyphenyl)diphenylphosphane with Phosphorus Halides – Crystal and Molecular Structure of (2-Hydroxyphenyl)diphenylphosphonium Bromide

1984 ◽  
Vol 39 (9) ◽  
pp. 1177-1184 ◽  
Author(s):  
Reinhard Schmutzler ◽  
Dietmar Schomburg ◽  
Rainer Bartsch ◽  
Othmar Stelzer
Keyword(s):  
Nmr Spectra ◽  
Crystal And Molecular Structure ◽  
Paramagnetic Complex ◽  
Coordination Geometry ◽  
Trimethylsilyl Derivative ◽  
Tetrahedral Coordination ◽  
Conductivity Data ◽  
H Nmr ◽  
Phosphorus Halides ◽  
Distorted Tetrahedral Coordination

Reaction of hexamethyldisilazane with (2-hydroxyphenyl)diphenylphosphane 1 affords the trimethylsilyl derivative 2-(Me3SiO)-C6H4-PPh2 (2). The Si-O-bond is cleaved by various phos­phorus halides, e.g. [Bun3PF]+ Br-, PhPCl2, PCl3, Ph2PF3 and PhPF4 with formation of the cor­responding P-O-derivatives and trimethylfluoro- or trimethylchlorosilane, respectively. The 31P{1H} NMR spectra of the products are discussed. [2-(Bun3PO)-C6H4-PPh2]+Br- (7) on reac­tion with nickel(II) bromide forms a paramagnetic complex of composition NiBr2L2 (L = 7). A distorted tetrahedral coordination geometry at Ni may be derived from its magnetic moment, electronic spectra and conductivity data. The structure of the hydrobromide of 1 shows strong hydrogen bonding between the OH- and PH-group of the cation and the bromide anion (P-H 1,42 Å, H···Br 2,41 Å, angle P-H···Br 150°; O-H 1,00 Å, H···Br 2,09 Å, angle O-H···Br 176°).

Synthesis and characterization of [MII(bqb)] (M = Co, Ni, Cu), [N(n-Bu)4][CoIII(bqb)(CN)2], and [N(n-Bu)4][CoIII(bqb)(N3)2] containing deprotonated N,N'-bis(2-quinolinecarboxamide)-1,2-benzene (bqb) – X-ray crystal structures of [NiII(bqb)] and [N(n-Bu)4][CoIII(bqb)(N3)2]

2006 ◽  
Vol 84 (7) ◽  
pp. 971-978 ◽  
Author(s):  
Soria Meghdadi ◽  
Mehdi Amirnasr ◽  
Vratislav Langer ◽  
Alison Zamanpoor
Keyword(s):  
Crystal Structures ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Square Planar ◽  
Distorted Octahedral ◽  
Elemental Analyses

Cobalt(II), nickel(II), copper(II), and two cobalt(III) complexes of a new dianionic ligand, bqb, [H2bqb = N,N'-bis(2-quinolinecarboxamide)-1,2-benzene] have been synthesized and characterized by elemental analyses, IR, and 1H NMR spectroscopy. The crystal and molecular structures of the [Ni(bqb)] (2) and [N(n-Bu)4][CoIII(bqb)(N3)2] (5) complexes were determined by X-ray crystallography. Complex 2 crystallizes in the monoclinic space group C2/c with a distorted square-planar structure including two short Ni–N (1.848 Å) and two long Ni–N (1.958 Å) bonds. The structure consists of sheets formed in the plane parallel to the b axis and diagonal to vectors a and c by intermolecular hydrogen bonds. Complex 5 crystallizes in the monoclinic space group C2 with a distorted octahedral structure. The [N(n-Bu)4]+ ion is disordered at the C3A and C4A atoms of one Bu. The IR and 1H NMR spectra of the complexes are also discussed.Key words: N4-dianionic amido ligand (bqb), (bqb) complexes of Co(II), Ni(II), Cu(II), and Co(III), azide, cyanide, X-ray crystal structures.

A new heteroleptic cuprous complex with strong yellow photoluminescence

2014 ◽  
Vol 70 (9) ◽  
pp. 858-861 ◽  
Author(s):  
Kaijie Xu ◽  
Mingwei Hong ◽  
Yicheng Zhang ◽  
Li Song ◽  
Wenxiang Chai
Keyword(s):  
Yellow Emission ◽  
Coordination Geometry ◽  
Tetrahedral Coordination ◽  
X Ray Diffraction ◽  
Acetonitrile Molecule ◽  
X Ray ◽  
Emission Signal ◽  
Ligand Charge Transfer ◽  
Distorted Tetrahedral Coordination ◽  
Cuprous Complex

In the title heteroleptic cuprous complex, (acetonitrile-κN)({2-[2-(diphenylphosphanyl)phenoxy]phenyl}diphenylphosphane-κ2P,P′)[2-(pyridin-4-yl-κN)-1,3-benzoxazole]copper(I) hexafluoridophosphate, [Cu(C36H28OP2)(CH3CN)(C12H8N2O)]PF6, conventionally abbreviated [Cu(POP)(CH3CN)(4-PBO)]PF6, where POP is the diphosphane ligand {2-[2-(diphenylphosphanyl)phenoxy]phenyl}diphenylphosphane and 4-PBO is the N-containing ligand 2-(pyridin-4-yl)-1,3-benzoxazole, the asymmetric unit consists of a hexafluoridophosphate anion and a whole mononuclear cation, where the CuIcentre is coordinated by two P atoms from the POP ligand, by one N atom from the 4-PBO ligand and by the N atom of the coordinated acetonitrile molecule, giving rise to a CuP2N2distorted tetrahedral coordination geometry. The electronic absorption, photoluminescence and thermal stability properties of this complex have been studied on as-synthesized samples, which had previously been examined by powder X-ray diffraction. A yellow emission signal is attributed to an excited state arising from metal-to-ligand charge transfer (MLCT).

Hydrolysis and condensation of chlorophosphine and alkyl phosphite ligands on platinum and palladium. 31P and 195Pt nuclear magnetic resonance studies and the crystal and molecular structures of [Pt2Cl4{μ-(EtO)2POP(OEt)2}2] and [Cl2Pt{μ-(P(OEt)2O)2P(O)}PtCl(PEt3)2]

1986 ◽  
Vol 64 (2) ◽  
pp. 343-352 ◽  
Author(s):  
David Eric Berry ◽  
Kathryn Anne Beveridge ◽  
Gordon William Bushnell ◽  
Keith Roger Dixon ◽  
Alan Pidcock
Keyword(s):  
Spin Systems ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray ◽  
H Nmr ◽  
Hydrolysis Of ◽  
Related Compounds ◽  
Alkyl Phosphite

Hydrolysis of cis-[PtCl2-{P(OEt)2Cl}2] results in condensation of the phosphite to form [Pt2Cl4{μ-(EtO)2POP(OEt)2}2], which crystallizes in the monoclinic space group P21/n, with a = 13.814(7), b = 11.429(4), c = 10.726(5) Å, β = 106.30(5)°. Reactions of P(OEt)2Cl or (EtO)2POP(OEt)2 with [Pt2Cl4(PEt3)2] also yield very easily hydrolyzed products but in these cases an even more complex condensation occurs to yield [Cl2Pt{(μ-(P(OEt)2O)2P(O)}PtCl(PEt3)2], which crystallizes in the monoclinic space group P21/c, a = 17.547(8), b = 19.775(6), c = 11.268(3) Å, β = 106.42(3)°. Complete X-ray diffraction studies are reported for both crystals, confirming the presence of double (EtO)2POP(OEt)2 bridges in [Pt2Cl4{(μ-(EtO)2POP(OEt)2}2] and a novel triphosphite bridge in [Cl2Pt{μ-(P(OEt)2O)2P(O)}PtCl(PEt3)2]. Detailed analyses and computer simulation of the 31P{1H} and 195Pt{1H} nmr spectra of these complexes are also described, together with studies of the related compounds, [Pt2Me4{μ-(EtO)2POP(OEt)2}2] and [Cl2(Et3P)Pt{μ-(EtO)2POP(OEt)2}PtCl2(PEt3)]. In conjunction with previous studies of [Pt2Cl2(dppm)2] and related complexes, these spectra provide examples of several types of AA′XX′ spin systems and the analysis of these systems is discussed in detail.

Complexes containing unsaturated medium rings: The crystal and molecular structures of two rhodium(I) complexes

1978 ◽  
Vol 31 (4) ◽  
pp. 781 ◽  
Author(s):  
R Mason ◽  
GR Scollary
Keyword(s):  
Molecular Structures ◽  
Monoclinic Space Group ◽  
Coordination Geometry ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
X Ray ◽  
Crystal And Molecular Structures ◽  
Square Planar ◽  
Medium Rings

The crystal and molecular structures of two rhodium(I) complexes with long-chain alkyne- or alkene-α,ω-diyldiphosphines have been determined by single-crystal X-ray diffraction techniques. RhCl(CO){But2P(CH2)4C≡C(CH2)4PBut2} crystallizes in the orthorhombic space group Pna21 with a 21.991 (2), b 11.915(1), c 11.890(1) Ǻ and Z 4. The structure was refined by least-squares methods to a conventional R factor of 0.097 for 1768 independent reflections (Mo Kα diffraction data). The rhodium ion is in a square-planar coordination geometry with trans-phosphorus atoms; the unsaturated (alkynyl) group is not bonded to the rhodium. Crystals of RhCl{But2P(CH2)2CH=CH(CH2)2- PBut2} are monoclinic, space group P21/c, a 20.783(12), b 8.580(4), c 14.799(9) Ǻ, β 100.70(2)°, Z 4. The structure analysis has converged to R 0.069 for 1417 reflections (Mo Kα diffractometry); the coordination geometry of the rhodium is again planar with the ethylenic group occupying a single bonding site. The effect of ring size on the rhodium-phosphorus bond lengths is discussed.

scholarly journals Tetrakis(dimethoxyboryl)methane

IUCrData ◽  
2016 ◽  
Vol 1 (8) ◽  
Author(s):  
Sumeng Liu ◽  
Gregory S. Girolami
Keyword(s):  
Title Compound ◽  
Coordination Geometry ◽  
Tetrahedral Coordination ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
Occupancy Factor ◽  
Bond Lengths ◽  
Methoxy Groups ◽  
Synthetic Intermediate ◽  
Distorted Tetrahedral Coordination

The title compound, tetrakis(dimethoxyboryl)methane (systematic name: octamethyl methanetetrayltetraboronate), C9H24B4O8or C[B(OMe)2]4, is a useful synthetic intermediate. Crystals of this compound at 102 K conform to the orthorhombic space groupPbcn. The molecules, which reside on sites of crystallographic twofold symmetry, have idealized -4 point symmetry like most other CX4molecules in which eachXgroup bears two non-H substituents at the 1-position. The central C atom has a slightly distorted tetrahedral coordination geometry, with C—B bond lengths of 1.5876 (16) and 1.5905 (16) Å. One of the methoxy groups is disordered over two sets of sites; the major component has an occupancy factor of 0.676 (8).

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