Synthesis, characterization, and X-ray structures of Rh(I) monocarbonyl complexes containing unsymmetric tridentate pyrazolylgallate ligands

1986 ◽  
Vol 64 (3) ◽  
pp. 566-574 ◽  
Author(s):  
David A. Cooper ◽  
Steven J. Rettig ◽  
Alan Storr
Keyword(s):  
Addition Reaction ◽  
Heavy Atom ◽  
Coordination Geometry ◽  
Space Group ◽  
X Ray ◽  
Square Planar ◽  
Text Interaction ◽  
Cl Atom ◽  
Centrosymmetric Dimers ◽  
Oxidative Addition Reaction

The reaction of the [Rh(CO)2Cl]2 dimer with the Na+[Me2Ga(N2C3H3)(OCH2(C5H4N))]− ligand has yielded the planar four-coordinate species [Me2Ga(N2C3H3)(OCH2(C5H4N))]Rh(CO), (LRh(CO)), displaying the tridentate gallate ligand in a meridional coordination mode. In addition, a second product, of similar geometry but with one of the Me groups on the Ga replaced by a Cl atom, viz, [(Cl)MeGa(N2C3H3)(OCH2(C5H4N))]Rh(CO), has also been isolated and characterized. The former complex undergoes a facile oxidative addition reaction with MeI, the transient six-coordinate Rh(III) species produced being rapidly converted, in a methyl migration step, to the five-coordinate Rh(III) acetyl complex, LRh(COMe)I. Crystals of [Me2Ga(N2C3H3)(OCH2(C5H4N))]Rh(CO) are monoclinic, a = 13.139(2), b = 13.324(2), c = 17.352(2) Å, β = 103.251(7)°, Z = 8, space group I2/a, and those of [(Cl)MeGa(N2C3H3)(OCH2(C5H4N))]Rh(CO) are triclinic, a = 8.846(2), b = 12.714(3), c = 7.631(2) Å, α = 93.82(1), β = 113.94(1), γ = 107.99(1)°, Z = 2, space group [Formula: see text] Both structures were solved by conventional heavy-atom methods and were refined by full-matrix least-squares procedures to final R values of 0.029 and 0.048 for 1890 and 1939 reflections with I ≥ 3σ(I), respectively. Both molecules display irregular square planar coordination geometry about Rh with Rh—O = 2.038(3) and 2.048(3), Rh—N(pyrazolyl) = 2.022(4) and 2.025(7), Rh—N(pyridyl) = 2.038(3) and 2.020(6), Rh—CO = 1.778(5) and 1.808(9) Å, respectively, for the two compounds. Molecules of [Me2Ga(N2C3H3)(OCH2(C5H4N))]Rh(CO) form weakly associated, centrosymmetric dimers via an intermolecular [Formula: see text] interaction of 3.5445(7) Å.

Coordination compounds containing a novel tridentate pyrazolylgallate ligand. X-ray structures of Me2Ga(μ-OH)(μ-Me2pz)GaMe2•HOCH2Me2pz and [Me2Ga(pz)(OCH2pz)]2Ni (pz = N2C3H3)

1988 ◽  
Vol 66 (1) ◽  
pp. 101-108 ◽  
Author(s):  
Arthur Mar ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Transition Metal Complexes ◽  
Heavy Atom ◽  
Direct Reaction ◽  
Coordination Geometry ◽  
The Novel ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Normal Bond ◽  
Cis Isomer

The syntheses of the novel anionic tridentate dimethyl(pyrazol-1-yl)(1-oxymethylpyrazolyl)gallate ligand and representative transition metal complexes thereof are reported. The direct reaction of Me3Ga with 1-hydroxymethyl-3,5-dimethylpyrazole leads to the isolation of Me2Ga(μ-OH)(μ-Me2pz)GaMe2•HOCH2Me2pz. Crystals of (μ-hydroxy)(μ-3,5-dimethylpyrazolyl)bis(dimethylgallium) 1-hydroxymethyl-3,5-dimethylpyrazole solvate are monoclinic, a = 33.105(2), b = 7.3048(7), c = 8.8336(6) Å, β = 97.474(7)°, Z = 4, space group P21/n, and those of bis[dimethyl(pyrazol-1-yl)(1-oxymethylpyrazolyl)gallato-N2,N2′,O]nickel(II) are monoclinic, a = 9.6345(3), b = 14.2731(6), c = 18.6356(7) Å, β = 99,660(3)°, Z = 4, space group P21/c. Both structures were solved by conventional heavy atom methods and were refined by full-matrix least-squares procedures to R = 0.044 and 0.037 for 2660 and 3904 reflections with I ≥ 3σ(I), respectively. Mean bond lengths in Me2Ga(μ-OH)(μ-Me2pz)GaMe2•HOCH2Me2pz are Ga—O = 1.918(11), Ga—N = 2.001(5), and Ga—C = 1.955(5) Å. Fac-[Me2Ga(pz)(OCH2pz)]2Ni crystallizes as an all-cis isomer with normal bond lengths and angles at Ga and Ni—O = 1.918(3) and 1.927(3), Ni—N = 2.030(4)–2.111(4) Å. The coordination geometry about Ni is irregular pseudo-octahedral with evidence of both steric and structural trans effects.

Synthesis of Bis(6-methylquinolin-8-yl)phenylarsine and tris(6-methylquinolin-8-yl)-arsine and certain of their bivalent palladium and zerovalent molybdenum complexes. Crystal and molecular structures of Dichloro- and Diiodo-[bis(6-methylquinolin-8-yl)phenylarsine]palladium(II)

1982 ◽  
Vol 35 (11) ◽  
pp. 2193 ◽  
Author(s):  
GL Roberts ◽  
BW Skelton ◽  
AH White ◽  
SB Wild
Keyword(s):  
Least Squares ◽  
Heavy Atom ◽  
Chelating Agent ◽  
Molecular Structures ◽  
Arsenic Trichloride ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Crystal And Molecular Structures ◽  
Square Planar

The potentially tridentate chelating agent bis(6-methylquinolin-8-yl)phenylarsine (AsN2) and quadridentate tris(6-methylquinolin-8-yl)arsine (AsN2) have been prepared from 6-methyl-8-lithio-quinoline and dichlorophenylarsine or arsenic trichloride, respectively. Both ligands behave as bidentates in complexes of the type [PdX2(AsN2)] and [PdX2(AsN2)] (where X = Cl or I) and as tridentates in [Mo(CO)3(AsN2)] and [Mo(CO)3(AsN2)]. The crystal and molecular structures of [PdCl2(AsN2)],CH2Cl2 and [PdI2(AsN2)] have been determined by single-crystal X-ray analysis. The dichloro complex crystallizes in space group P1 (Ci1; No.2) with a 9.963(3), b 8.555(3), c 16.102(7) �; α 86.64(3), β 82.13(3), γ 85.84(3)�; U 1354.3(9) �3 and Z = 2. The structure was solved by heavy-atom methods and refined by least squares to R 0.044 for 2530 'observed' reflections with 1>3σ(I). The coordination geometry of the palladium(II) atom is pseudo-square-planar in which the potentially tridentate AsN2 is behaving as a bidentate only. There is no evidence of interaction of the remaining 6-methylquinolin-8-yl group with the metal centre, although a weak interaction between the solvent of crystallization and the metal may be present. The diiodo complex similarly crystallizes in the centrosymmetric triclinic space group P1 (Cil ; No.2) with a 13.590(5), b 10.035(2), c 9.435(2) �; α 102.68(2), β 90.10(2), γ 92.99(2)�; U 1253.5(6) �3 and Z = 2. Least- squares refinement led to a convergence with R 0.038 for 3461 'observed' reflections. The structure of this complex was similar to that of the dichloro analogue.

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.

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.

Synthesis and structural studies of rhodium complexes of phosphorus—sulfur ligands

1986 ◽  
Vol 64 (9) ◽  
pp. 1870-1875 ◽  
Author(s):  
David G. Dick ◽  
Douglas W. Stephan
Keyword(s):  
Single Crystal ◽  
Planar Geometry ◽  
Methyl Groups ◽  
Rhodium Complexes ◽  
Coordination Geometry ◽  
Structural Studies ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray ◽  
Square Planar

Rhodium complexes of the phosphorus—sulfur ligands, 2-diphenylphosphinoethyl methyl sulfide (MeSP), 1, and 2-diphenylphosphinothiophene (PTH), 2, have been prepared and studied by single crystal X-ray diffraction methods. [Rh(MeSP)2]BF4•H2O, 3, crystallizes in the space group P21/n with a = 16.939(6) Å, b = 17.152(5) Å, c = 12.049(9) Å, β = 106.50(4)°, and Z = 4. The MeSP ligands chelate to Rh yielding a distorted square-planar geometry. The disposition of the methyl groups on the cis sulfur atoms is transoid. Average Rh—P and Rh—S bond distances were found to be 2.225(3) and 2.347(3) Å, respectively. [Rh(PTH)2(COD)]BF4, 4, crystallizes in the space group Cc with a = 15.862(2) Å, b = 15.112(3) Å, c = 16.029(3) Å, β = 103.32(1)°, and Z = 4. The Rh atom in 4 also has essentially a square-planar coordination geometry. 2 does not chelate but rather is monohapto through phosphorus. Rh—P distances of 2.319(3) and 2.378(3) Å and Rh—C distances of 2.17(1), 2.22(1), 2.24(1), and 2.27(1) Å were found. The small variations in the Rh—P and Rh—C bonds distances appear to be a result of steric interactions between 2 and the COD ligand.

The Crystal and Molecular Structures of Two Modifications of cis-Dichloro-mer-tris-(dimethylphenylphosphine)hydridoiridium(III)

1988 ◽  
Vol 41 (3) ◽  
pp. 283 ◽  
Author(s):  
GB Robertson ◽  
PA Tucker
Keyword(s):  
Heavy Atom ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Metal Ligand ◽  
Ligand Bond

The structures of two crystalline modifications of mer -(Pme2Ph)3H-cis-Cl2IrIII, (1), have been determined from single-crystal X-ray diffraction data. Modification (A) is monoclinic, space group P21/c with a 12.635(1), b 30.605(3), c 14.992(2)Ǻ, β 110.01(2)° and Z = 8. Modification (B) is orthorhombic, space group Pbca with a 27.646(3), b 11.366(1), c 17.252(2)Ǻ and Z = 8. The structures were solved by conventional heavy atom techniques and refined by full-matrix least- squares analyses to conventional R values of 0.037 [(A), 8845 independent reflections] and 0.028 [(B), 5291 independent reflections]. Important bond lengths [Ǻ] are Ir -P(trans to Cl ) 2.249(1) av. (A) and 2.234(1) (B), Ir -P(trans to PMe2Ph) 2.339(2) av. (A) and 2.344(1), 2.352(1) (B), Ir-Cl (trans to H) 2.492(2), 2.518(2) (A) and 2.503(1) (B) and Ir-Cl (trans to PMe2Ph)2.452(2) av. (A) and 2.449(1)(B). Differences in chemically equivalent metal- ligand bond lengths emphasize the importance of non-bonded contacts in determining those lengths.

Silver(I)-Saccharinato Complexes with 2-(Aminomethyl)pyridine and 2-(2-Aminoethyl)pyridine Ligands: [Ag(sac)(ampy)] and [Ag2(sac)2(μ-aepy)2]

2005 ◽  
Vol 60 (9) ◽  
pp. 978-983 ◽  
Author(s):  
Sevim Hamamci ◽  
Veysel T. Yilmaz ◽  
William T. A. Harrison
Keyword(s):  
Thermal Analysis ◽  
Hydrogen Bonds ◽  
Monoclinic Space Group ◽  
Stacking Interactions ◽  
Coordination Geometry ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Pyridine Ligands

Two new saccharinato-silver(I) (sac) complexes, [Ag(sac)(ampy)] (1), and [Ag2(sac)2(μ-aepy)2] (2), [ampy = 2-(aminomethyl)pyridine, aepy = 2-(2-aminoethyl)pyridine], have been prepared and characterized by elemental analysis, IR spectroscopy, thermal analysis and single crystal X-ray diffraction. Complexes 1 and 2 crystallize in the monoclinic space group P21/c and triclinic space group P1̄, respectively. The silver(I) ions in both complexes 1 and 2 exhibit a distorted T-shaped AgN3 coordination geometry. 1 consists of individual molecules connected into chains by N-H···O hydrogen bonds. There are two crystallographically distinct dimers in the unit cell of 2 and in each dimer, the aepy ligands act as a bridge between two silver(I) centers, resulting in short argentophilic contacts [Ag1···Ag1 = 3.0199(4) Å and Ag2···Ag2 = 2.9894(4) Å ]. Symmetry equivalent dimers of 2 are connected by N-H···O hydrogen bonds into chains, which are further linked by aromatic π(py)···π(py) stacking interactions into sheets.

Übergangsmetallkomplexe mit Schwefelliganden, LXXVI Redox- und Additionsreaktionen von Nickelkomplexen mehrzähniger Thioether-Thiolat-Liganden. Röntgenstrukturanalysen von (NMe4)2[Ni(′S2′)2] und [Ni(′S4 – C3′)(PMe3)] / Transition Metal Complexes with Sulfur Ligands, LXXVI Redox and Addition Reactions of Nickel Complexes with Multidentate Thioether-Thiolato Ligands. X-Ray Structure Determinations of (NMe4)2[Ni(′S2′)2] and [Ni(′S4–C3′)(PMe3)]

1991 ◽  
Vol 46 (12) ◽  
pp. 1601-1608 ◽  
Author(s):  
Dieter Sellmann ◽  
Stefan Fünfgelder ◽  
Falk Knoch ◽  
Matthias Moll
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Structure Analysis ◽  
Transition Metal Complexes ◽  
Nickel Complexes ◽  
Addition Reactions ◽  
Coordination Geometry ◽  
X Ray ◽  
Square Planar ◽  
Structure Determinations

In order to elucidate specific properties of nickel sulfur complexes, redox and addition-elimination reactions of [Ni(′OS4')]2, [Ni(′NHS4')]2, [Ni(′S5')], [Ni('S4—C5')], and [Ni('S4—C3')] were investigated ('OS4′ 2' = 2,2'-bis(2-mercaptophenylthio)diethylether(2—), 'NHS4'2- = 2,2'-bis(2-mercaptophenylthio)diethylamine(2—), 'S5'2- = 2,2'-bis(2-mercaptophenylthio)diethylsulfide(2—), 'S4-C5'2- = 1,5-bis(2-mercaptophenylthio)pentane(2—), 'S4—C3'2- = 1,3-bis(2-mercaptophenylthio)propane(2—)).Cyclovoltammetry proves the complexes to be redox inactive between —1.4 and +0.8 V vs. NHE. Above +0.8 V the complexes are irreversibly oxidized, below —1,4 V desalkylation takes place and [Ni(′S,′)2]2- is formed. An X-ray structure analysis was carried out of (NMe4)2[Ni(′S2')2], which shows a planar anion with the Ni center in a nearly perfect square planar coordination. Distances and angles are practically identical to those in the [Ni(′S2')2-] monoanion.The complexes coordinate only phosphines as coligands, but thioether donors simultaneously decoordinate and, dependant of reaction temperature, mono- or trisphosphine complexes are formed. [Ni(′S4—C3')(PMe3)] was characterized by X-ray structure analysis and exhibits a square pyramidal coordination geometry.

Thiocarbonyl Complexes of Rhenium. Part I.

1993 ◽  
Vol 48 (6) ◽  
pp. 771-777 ◽  
Author(s):  
Ulrich Abram ◽  
Bernd Lorenz
Keyword(s):  
Mass Spectrometry ◽  
Nmr Spectroscopy ◽  
Coordination Geometry ◽  
X Ray Diffraction ◽  
Rhenium Atom ◽  
Space Group ◽  
X Ray ◽  
Monomeric Complex ◽  
Structure Solution ◽  
R Value

Novel rhenium complexes with terminal thiocarbonyl groups have been synthesized from ReCl3(Me2PhP)3 and sodium diethyldithiocarbamate. mer-(Diethyldithiocarbamato)tris-(dimethylphenylphosphine)(thiocarbonyl)rhenium(I), mer-[Re(CS)(Me2PhP)3(Et2dtc)], and tris(diethyldithiocarbamato)(thiocarbonyl)rhenium(III), [Re(CS)(Et2dtc)3] have been studied by infrared and NMR spectroscopy, mass spectrometry and X-ray diffraction.mer-[Re(CS)(Me2PhP)3(Et2dtc)] crystallizes orthorhombic in the space group Pna21 with a = 1516.1(2), b = 2189.8(2) and c = 1035.6(1) pm. Structure solution and refinement converged at R = 0.042. The coordination geometry is a distorted octahedron. The Re—C bond length is found to be 184(2) pm.[Re(CS)(Et2dtc)3] crystallizes monoclinic in the space group P21/c with a = 962.2(6), b = 1744.0(2), c = 1537.4(6) pm and β = 96.21(1)°. The final R value is 0.028. In the monomeric complex the rhenium atom is seven-coordinate with an approximate pentagonal-bipyramidal coordination sphere and a rhenium-carbon distance of 181(1) pm.

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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