Allylic derivatives of nickel and palladium

1981 ◽  
Vol 59 (6) ◽  
pp. 996-1006 ◽  
Author(s):  
Kenneth S. Chong ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Least Squares ◽  
Trinuclear Complex ◽  
Boat Conformation ◽  
Coordination Geometry ◽  
Orientational Disorder ◽  
Full Matrix ◽  
Space Group ◽  
Coordination Sites ◽  
Square Planar ◽  
Derivatives Of

The synthesis of novel allylic derivatives of Ni and Pd incorporating the bispyrazolylgallate ligand Me2Ga(N2C5H7)2− is described. Pyrazolyl-bridged homobinuclear and trinuclear nickel allyl systems are also presented. Crystal structures of [Me2Ga(N2C5H7)2]Ni(η3-C3H5) and [(η3-C3H5)Ni(N2C5H7)2]2Ni are described. Crystals of the former are triclinic, a = 8.265(1), b = 10.487(1), c = 11.755(2) Å, α = 72.60(1), β = 87.28(1), γ = 67.58(1)°, Z = 2, space group [Formula: see text] and crystals of the latter are monoclinic, a = 7.9172(3), b = 10.6929(1), c = 16.9118(6) Å, β = 102.887(2)°, Z = 2, space group P21/c. Both structures were solved by Patterson and Fourier syntheses and were refined by full-matrix least-squares procedures to R = 0.026 and 0.025 for 3329 and 2914 reflections with I ≥ 3σ(I) respectively. In both structures the M—(N—N)2—M rings are in the boat conformation and the allyl groups display twofold orientational disorder. In [Me2Ga(N2C5H7)2]Ni(η3-C3H5) the nickel coordination may be regarded as square-planar with the allyl ligand occupying two coordination sites and the coordination about the gallium is distorted tetrahedral. Important bond lengths (corrected for libration) are: Ni—N, 1.926(2) and 1.929(2), Ni—C, 1.971(5)–2.025(3), Ga—N, 1.994(2) and 1.996(2), Ga—C, 1.966(3) and 1.988(3) Å. The trinuclear complex [(η3-C3H5)Ni(N2C5H7)2]2Ni is centrosymmetric with the central Ni(1) atom bonded to four pyrazolyl nitrogen atoms in square-planar fashion. The outer Ni(2) atom is bonded to two pyrazolyl nitrogens and to an allyl group and also has square-planar coordination geometry. Important bond distances in this complex are: Ni(1)—N, 1.897(1) and 1.901(1), Ni(2)—N, 1.908(2) and 1.912(2), Ni(2)—C, 1.97(l)–2.022(3) Å.

Synthesis and characterization of [Me2Ga(3,5-Me2pz)2]Rh(CO)PPh3 and the X-ray structure of its toluene solvate

1985 ◽  
Vol 63 (2) ◽  
pp. 503-508 ◽  
Author(s):  
Brenda M. Louie ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Physical Properties ◽  
Least Squares ◽  
Heavy Atom ◽  
Synthesis And Characterization ◽  
Boat Conformation ◽  
Full Matrix ◽  
Space Group ◽  
X Ray ◽  
Square Planar

Details of the synthesis and physical properties of [Me2Ga(3,5-Me2pz)2]Rh(CO)PPh3 are given. Crystals of [dimethylbis(3,5-dimethyl-1-pyrazolyl)gallato-N,N′](triphenylphosphine)carbonylrhodium(I) – toluene (1:1) are triclinic, a = 10.690(2), b = 12.928(2), c = 13.998(2) Å, α = 77.44(1), β = 83.50(1), γ = 72.70(1)°, Z = 2, space group [Formula: see text]. The structure was solved by conventional heavy-atom methods and was refined by full-matrix least-squares procedures to R = 0.039 and Rw = 0.048 for 5987 reflections with I ≥ 3σ(I). The Rh(I) is in a distorted square planar environment with Rh—N = 2.090(3) and 2.097(2), Rh—CO = 1.815(4), and Rh—P = 2.2700(8) Å. The central six-membered RhGaN4 ring has a steep boat conformation with a [Formula: see text] separation of 3.3819(4) Å.

Crystal and molecular structure of [dimethyl(1-pyrazolyl)(2-pyridyl-methoxy)gallato-N2,O,N3](η3-allyl)dicarbonylinolybdenum(II)

1988 ◽  
Vol 66 (3) ◽  
pp. 355-358 ◽  
Author(s):  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Molecular Structure ◽  
Nitrogen Atom ◽  
Least Squares ◽  
Crystal And Molecular Structure ◽  
Heavy Atom ◽  
Coordination Geometry ◽  
Pyridyl Nitrogen ◽  
Full Matrix ◽  
Space Group ◽  
Bond Lengths

Crystals of [dimethyl(1-pyrazolyl)(2-pyridylmethoxy)gallato-N2,O,N3](η3-allyl)dicarbonylmolybdenum(II) are triclinic, a = 9.632(2), b = 9.798(2), c = 10.255(2) Å, α = 80.16(1), β = 87.38(1), γ = 81.75(1)°, Z = 2, space group [Formula: see text]. The structure was solved by conventional heavy-atom methods and was refined by full-matrix least-squares procedures to R = 0.033 and Rw = 0.037 for 3000 reflections with I ≥ 3σ(I). The molecule has pseudo-octahedral coordination geometry with the tridentate [Me2Ga(N2C3H3)(OCH2(C5H4N))]− ligand facially coordinated and the η3-allyl ligand occupying one coordination site trans to the pyridyl nitrogen atom. Important bond lengths are Mo—O = 2.219(2), Mo—N(py) = 2.212(3), Mo—N(pz) = 2.232(2), Mo—C(allyl) = 2.290(4), 2.189(4), 2.341(4), Mo—CO (trans to O) = 1.928(4), and Mo—CO (trans to N) = 1.952(4) Å.

Zinc 3,5-dimethylpyrazolate complexes: synthesis and structural studies. The crystal and molecular structure of [Zn2(dmpz)4(Hdmpz)2]

1990 ◽  
Vol 68 (9) ◽  
pp. 1494-1498 ◽  
Author(s):  
Martin K. Ehlert ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
Robert C. Thompson ◽  
James Trotter
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Least Squares ◽  
Crystal And Molecular Structure ◽  
Heavy Atom ◽  
High Yield ◽  
Coordination Geometry ◽  
Structural Studies ◽  
Full Matrix ◽  
Space Group

Zinc metal reacts with excess 3,5-dimethylpyrazole (Hdmpz) in the presence of O2 to produce materials of composition Zn(dmpz)2(Hdmpz)y. Thermolysis of these materials results in the loss of Hdmpz and the formation of the [Zn(dmpz)2]x polymer. Under appropriate conditions the pure dimer [Zn2(dmpz)4(Hdmpz)2] can be obtained in high yield. Crystals of bis[μ-(3,5-dimethylpyrazolyl-N1,N2)]bis[(3,5-dimethylpyrazolyl)(3,5-dimethylpyrazole)zinc(II)] are orthorhombic, a = 17.009(2), b = 29.239(2), c = 13.590(2) Å, Z = 8, space group Fddd. The structure was solved by heavy atom methods and was refined by full-matrix least-squares procedures to R = 0.037 and Rw = 0.042 for 913 reflections with I ≥ 3σ(I). The structure of [Zn2(dmpz)4(Hdmpz)2] contains nearly planar doubly dmpz bridged Zn2 units capped at each end by strongly hydrogen-bonded [Formula: see text] units. The zinc atoms display pseudotetrahedral coordination geometry with Zn—N = 1.991(3) (bridging) and 2.025(3) Å (terminal), and N—Zn—N = 99.6(2)–113.8(2)°. Keywords: zinc 3,5-dimethylpyrazolate complexes, crystal structure.

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

1979 ◽  
Vol 57 (23) ◽  
pp. 3090-3098 ◽  
Author(s):  
Kenneth S. Chong ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Least Squares ◽  
Nucleophilic Attack ◽  
Donor Ligands ◽  
Nickel Compound ◽  
Neutral Donor ◽  
Full Matrix ◽  
Space Group ◽  
Nitrosyl Complexes ◽  
Square Planar

A series of neutral pyrazolyl-bridged nickel nitrosyl complexes, [LNi(NO)]2 (where L = pyrazolyl, N2C3H3; 3,5-dimethylpyrazolyl, N2C5H7; or 3,5-di-tert-butylpyrazolyl, N2C11H19), is described. The nickel atoms are susceptible to nucleophilic attack and the reactivity of the dimers with neutral donor ligands is reported. In addition to the dimeric molecules a novel trimetallic nickel compound [(ON)Ni(N2C5H7)2]2Ni has also been isolated. Crystals of [Ni(NO)(N2C5H7)]2 are monoclinic, a = 18.925(2), b = 11.012(1), c = 7.037(2) Å, β = 100.93(1)°, Z = 4, space group C2/c and crystals of [(ON)Ni(N2C5H7)2]2Ni are triclinic, a = 7.4041(7), b = 9.6331(7), c = 9.7595(8) Å, α = 85.698(9), β = 73.174(8), γ = 76.109(8)°, Z = 1, space group [Formula: see text]. Both structures were solved by Patterson and Fourier syntheses and were refined by full-matrix least-squares procedures to R = 0.035 and 0.028 for 832 and 2128 reflections with I ≥ 3σ(I) respectively. Nearly planar centrosymmetric molecules of [Ni(NO)(N2C5H7)]2 contain trigonal planar nickel atoms with Ni—N(pyrazolyl) = 1.880(3) and 1.922(3), Ni—NO = 1.616(4), and N—O = 1.158(4) Å, Ni—N—O = 178.9(4)°. This structure also contains an unusually long N—N bond in the pyrazolyl ring (1.463(4) Å). Centrosymmetric molecules of [(ON)Ni(N2C5H7)2]2Ni contain a central square-planar Ni(II) atom bonded to four pyrazolyl nitrogen atoms (mean Ni—N = 1.905(1) Å) and two trigonal planar outer nickel atoms coordinated to two pyrazolyl nitrogen atoms (mean Ni—N = 1.922(3) Å) and to a somewhat bent nitrosyl group (Ni—N = 1.625(3), N—O = 1.153(4) Å, Ni—N—O = 168.9(3)°).

Catalytic decarbonylation of aldehydes using iron(II) porphyrin complexes, and the crystal structure of (5,10,15,20-tetraphenylporphinato)bis(tri-n-butylphosphine)iron(II)

1988 ◽  
Vol 66 (8) ◽  
pp. 2072-2078 ◽  
Author(s):  
Ramesh M. Belani ◽  
Brian R. James ◽  
David Dolphin ◽  
Steven J. Rettig
Keyword(s):  
Crystal Structure ◽  
Least Squares ◽  
Hydrogen Abstraction ◽  
Heavy Atom ◽  
Crystal Form ◽  
Coordination Geometry ◽  
Full Matrix ◽  
Space Group ◽  
Initiation Reaction ◽  
Trace Water

The complex (5, 10, 15, 20-tetraphenylporphinato)bis(tri-n-butylphosphine)iron(II), 1, has been isolated in a triclinic crystal form, a = 12.499(3), b = 12.528(2), c = 12.039(2) Å, α = 116.39(1), β = 109.79(1), γ = 98.13(1)°, Z = 1, space group [Formula: see text]. The structure was solved by conventional heavy atom methods and was refined by full-matrix least-squares procedures to R = 0.060 and Rw = 0.070 for 3551 reflections with I ≥ 3σ(I). The molecule, which has crystallographic [Formula: see text], symmetry, displays a relatively undistorted pseudo-octahedral coordination geometry with Fe—P = 2.346(1) and Fe—N = 1.998(3) and 1.993(3) Å. In CH2Cl2 solution, 1 reacts with CO and aldehydes to generate the carbonyl(phosphine) derivative, and decarbonylation of phenylacetaldehyde to toluene becomes catalytic under an Ar stream. The aldehyde decarbonylations involve radical pathways via carbonyl loss from [Formula: see text]. The hydrogen abstraction/initiation reaction probably utilizes trace O2 (and possibly trace (water); speculative mechanisms are discussed.

Studies in aryltin chemistry. Part 6. Crystal and molecular structures of tetra(p-methylsulphonylphenyl)tin(IV) and tetra(p-methylsulphinylphenyl)tin(IV) monohydrate

1990 ◽  
Vol 68 (8) ◽  
pp. 1277-1282 ◽  
Author(s):  
Ivor Wharf ◽  
Michel G. Simard ◽  
Henry Lamparski
Keyword(s):  
Least Squares ◽  
Crystal Structures ◽  
Direct Method ◽  
Molecular Structures ◽  
Water Molecules ◽  
Monoclinic Space Group ◽  
Molecular Symmetry ◽  
Asymmetric Unit ◽  
Full Matrix ◽  
Space Group

Tetrakis(p-methylsulphonylphenyl)tin(IV) and tetrakis(p-methylsulphinylphenyl)tin(IV) n-hydrate have been prepared and their spectra (ir 1350–400 cm−1; nmr, 1H, 13C, 119Sn) and X-ray crystal structures are reported. The first compound is monoclinic, space group C2/c, Z = 4, with a = 21.589(6), b = 6.207(3), c = 22.861(11) Å, β = 93.80(3)° (22 °C); the structure was solved by the direct method and refined by full-matrix least squares calculations to R = 0.043 for 2755 observed reflections. It has 2 molecular symmetry with the methyl group and one oxygen atom completely disordered in both CH3S(O2) groups in the asymmetric unit. The second compound is tetragonal, space group P42/n, Z = 2, with a = b = 15.408(6), c = 6.379(2) Å (−100 °C); the structure was solved by the Patterson method and refined by full-matrix least squares calculations to R = 0.060 for 1209 observed reflections. It has [Formula: see text] molecular symmetry with the whole asymmetric unit disordered. Water molecules occupy positions on parallel 42 axes but molecular packing requirements prevent all sites having 100% occupancy giving n ~ 1 for the hydrate. Keywords: Tetra-aryltins, crystal structures, sulphone, sulphoxide, hydrogen-bonding.

Synthesis, Characterization and Biological Activity Evaluation of Novel Pd(II) and Pt(II) Complexes with Heterocyclic Hydrazone Ligands

2007 ◽  
Vol 555 ◽  
pp. 423-427 ◽  
Author(s):  
Nenad R. Filipović ◽  
Tamara R. Todorović ◽  
D.M. Sladić ◽  
Irena T. Novaković ◽  
D.A. Jeremić ◽  
...  
Keyword(s):  
Biological Activity ◽  
13C Nmr Spectroscopy ◽  
Chloride Ions ◽  
Planar Geometry ◽  
Moderate Activity ◽  
Coordination Sites ◽  
Ligand Type ◽  
Square Planar ◽  
Derivatives Of ◽  
Hydrazone Ligands

New complexes of Pt(II) with condensation derivatives of ethyl hydrazinoacetate and either 2-acetylpyridine or 2-quinolinecarboxaldehyde, and of Pd(II) with the condensation derivative of ethyl hydrazinoacetate and 2-quinolinecarboxaldehyde were synthesized and characterized by elemental analysis, IR, 1H- and 13C-NMR spectroscopy, and molar conductivity measurements. The complexes have a square planar geometry, ligands binding as bidentates in the neutral form, and the remaining two coordination sites being occupied by chloride ions. Biological activity of new complexes, and of previously synthesized Pd(II), Cd(II), Co(III) and Zn(II) complexes with this ligand type was evaluated by the brine shrimp test. All the complexes showed a moderate activity.

Structural studies of organoboron compounds. XX.(Salicylaldoximato-O,N)diphenylboron

1984 ◽  
Vol 62 (7) ◽  
pp. 1363-1368 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Hydrogen Bonds ◽  
Least Squares ◽  
Chelate Ring ◽  
Direct Methods ◽  
Structural Studies ◽  
Organoboron Compounds ◽  
Full Matrix ◽  
Space Group ◽  
Bond Lengths ◽  
Phenolic Oxygen

Crystals of (salicylaldoximato-O,N)diphenylboron are triclinic, a = 10.125(2), b = 10.797(1), c = 14.760(2) Å, α = 89.05(1), β = 86.98(1), γ = 83.18(1)°, Z = 4, space group [Formula: see text]. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.040 and Rw = 0.048 for4145 reflections with I ≥ 3σ(I). The structure consists of two crystallographically independent, but essentially identical, molecules linked by strong [Formula: see text] hydrogen bonds to form continuous spirals along the a axis. The Ph2B moiety is chelated by the phenolic oxygen and oxime nitrogen atoms of the ligand resulting in the formation of a non-planar six-membered chelate ring. Important libration-corrected mean bond lengths are O—B = 1.516(1), N—B = 1.609(2), and C—B = 1.613(2) Å.

scholarly journals Di-μ-chlorido-bis{[2-(di-tert-butylphosphanyl)biphenyl-3-yl-κ2C3,P]palladium(II)} dichloromethane disolvate

2013 ◽  
Vol 69 (2) ◽  
pp. m86-m86 ◽  
Author(s):  
Cedric W. Holzapfel ◽  
Bernard Omondi
Keyword(s):  
Palladium Complex ◽  
Solvent Molecule ◽  
Membered Ring ◽  
The Other ◽  
Coordination Geometry ◽  
Inversion Center ◽  
Asymmetric Unit ◽  
Coordination Sites ◽  
Square Planar ◽  
Cl Atoms

The asymmetric unit of the title compound, [Pd2Cl2(C20H26P)2]·2CH2Cl2, contains one half-molecule of the palladium complex and a dichloromethane solvent molecule. In the complex, two PdIIatoms are bridged by two Cl atoms, with the other two coordination sites occupied by a C atom of the biphenyl system and a P atom, resulting in a distorted square-planar coordination geometry of the PdIIatom and a cyclometallated four-membered ring. The Pd2Cl2unit is located about an inversion center. The planes of the rings of the biphenyl system make a dihedral angle of 66.36 (11)°.

Perchlorate and difluorophosphate coordination derivatives of rhenium carbonyl

1980 ◽  
Vol 33 (11) ◽  
pp. 2369 ◽  
Author(s):  
E Horn ◽  
MR Snow
Keyword(s):  
Heavy Atom ◽  
Coordination Geometry ◽  
X Ray Diffraction ◽  
Metal Centre ◽  
Triclinic Space Group ◽  
Full Matrix ◽  
X Ray ◽  
Rhenium Carbonyl ◽  
Hydrolysis Of ◽  
Derivatives Of

The complexes Re(CO)5ClO4, Re(CO)5PO2F2, L2(CO)3Re(OClO3) and L2(CO)3Re(PO2F2), where L2 = 2,2?-bipyridyl (bpy), have been synthesized by bromide abstraction reactions from the respective rhenium carbonyl bromide precursors. The complexes were characterized by infrared and mass spectroscopy. The crystal structure of (bpy)(CO)3Re(PO2F2) has been determined from X-ray diffraction data by the heavy-atom technique. The crystals are triclinic, space group Pī with a 8.620(3), b 15.912(5), c 6.466(3) Ǻ, α 102.08(8), β 83.29(8), γ 95.08(4) and Z 2. The structure has been refined by full-matrix least-squares from 2829 reflections to R = 0.084, Rw = 0.088. The coordination geometry about rhenium is that of a distorted octahedron. Difluorophosphate coordinates to the metal centre by one of its oxygen atoms. Formation of the difluorophosphate by hydrolysis of hexafluorophosphate was shown by 31P n.m.r. spectra.

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