Synthesis and characterization of LMo(CO)3M(PPh3)x (where L = tridentate pyrazolyl-gallate or -borate ligand; M = Rh, x = 2; M = Cu, x = 1). X-ray crystal structures of [MeGapz3]Mo(CO)3Rh(PPh3)2 and [MeGapz3]Mo(CO)3Cu(PPh3) (where pz = pyrazolyl, N2C3H3)

1986 ◽  
Vol 64 (2) ◽  
pp. 373-386 ◽  
Author(s):  
Gregory A. Banta ◽  
Brenda M. Louie ◽  
Emmanuel Onyiriuka ◽  
Steven J. Rettig ◽  
Alan Storr
Keyword(s):  
Least Squares ◽  
Crystal Structures ◽  
Heavy Atom ◽  
Synthesis And Characterization ◽  
Octahedral Structure ◽  
Full Matrix ◽  
Space Group ◽  
X Ray

The reactions of the LMo(CO)3− ions (L = MeGapz3, HBpz3, Me2Gapz(OCH2CH2NMe2)) with [Cu(PPh3)Cl]4 and Rh(PPh3)3Cl have yielded complexes with Mo—Cu and Mo—Rh bonds. The X-ray crystal structures of two such complexes have been determined. Crystals of [MeGapz3]Mo(CO)3Cu(PPh3) are monoclinic, a = 17.071(2), b = 16.738(1), c = 23.641(3) Å, β = 104.899(6)°, Z = 8, space group P21/n, and those of [MeGapz3]Mo(CO)3Rh(PPh3)2, are triclinic, a = 12.519(3), b = 17.182(4), c = 12.071(2) Å, α = 105.02(1), β = 109.87(1), γ = 97.10(2)°, 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 R = 0.040 and Rw = 0.035 for 6296 reflections with I ≥ 2σ(I) and R = 0.036 and Rw = 0.037 for 5642 reflections with I ≥ 3σ(I), respectively. The former complex provides a rare example of a 3:3:1, or capped octahedral structure, with a short (mean) Mo—Cu distance of 2.513(9) Å. The latter compound displays one terminal and two bridging CO ligands and a Mo—Rh distance of 2.6066(5) 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.

Synthesis and characterization of homoleptic ruthenium(II) imidazole complexes, and a carbonyl species derived by CO abstraction from DMF

1998 ◽  
Vol 76 (10) ◽  
pp. 1379-1388 ◽  
Author(s):  
Ian R Baird ◽  
Steven J Rettig ◽  
Brian R James ◽  
Kirsten A Skov
Keyword(s):  
Ambient Temperature ◽  
Least Squares ◽  
Key Words ◽  
Elemental Analysis ◽  
Synthesis And Characterization ◽  
Full Matrix ◽  
Space Group ◽  
X Ray ◽  
Imidazole Complexes

[Ru(II)(L)6]2+ complexes were synthesized from [Ru(DMF)6][CF3SO3]3; DMF = dimethylformamide, L = imidazole (Im), N-methylimidazole (NMeIm) and 5-methylimidazole (5MeIm). The 2-methylimidazole complex trans-[Ru(CO)(DMF)(2MeIm)4][CF3SO3]2 (4) was also synthesized via a reaction involving abstraction of CO from DMF; 4 loses CO reversibly at ambient temperature to form [Ru(DMF)(2MeIm)4][CF3SO3]2 (5), and the DMF can be removed to generate a [Ru(CF3SO3)x(2MeIm)4][CF3SO3]y species (x = 2, y = 0, or x = 1 = y), containing coordinated triflate. The complexes were characterized by elemental analysis, conductivity, UV-vis, NMR, and IR spectroscopies. The structures of [Ru(Im)6][CF3SO3]2 (1), [Ru(NMeIm)6][CF3SO3]2 (2), and [Ru(5MeIm)6][CF3SO3]2 (3) were established by X-ray crystallographic analyses. Crystals of 1, are triclinic, a = 7.4010(6), b = 9.9846(15), c = 11.275(2) Å, α = 113.469(5), β = 92.419(2), γ = 94.737(2)°, Z = 1, space group P1 ; those of 2, are trigonal, a = 11.558(2), c = 8.109(3) Å, Z = 1, space group P3; and those of 3, are trigonal, a = 12.6547(4), c = 20.4078(12) Å, Z = 3, space group R3. The structures were solved by Patterson methods and refined by full-matrix least-squares procedures to R(F) = 0.029, 0.034, and 0.034 (R w (F2) = 0.055, R w (F) = 0.031, and R w (F2) = 0.058), respectively. Key words: hexakis(imidazole)ruthenium(II) triflates, crystal structures, CO abstraction.

Pyrazagaboles, pyrazolyl-bridged heterocycles containing boron and gallium

1990 ◽  
Vol 68 (1) ◽  
pp. 59-63 ◽  
Author(s):  
Steven J. Rettig ◽  
Mark Sandercock ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Least Squares ◽  
Crystal Structures ◽  
Structural Characterization ◽  
Heavy Atom ◽  
Full Matrix ◽  
Space Group ◽  
The Mean

The synthesis and structural characterization of representative and novel pyrazagaboles, boron- and gallium-containing compounds with a central six-membered heterocyclic B—(N—N)2—Ga ring feature, are detailed. Crystals of dimethylgallium-bis(μ-pyrazolyl)dimethylboron are orthorhombic, a = 7.6135(5), b = 16.2917(5), c = 22.331(1) Å, Z = 8, space group Pbca, and those of hydroxy(methyl)galliumbis(μ-pyrazolyl)dimethylboron are orthorhombic, a = 7.6197(3), b = 16.2184(7), c = 22.190(1) Å, Z = 8, space group Pbca. Both structures were solved by conventional heavy atom methods and were refined by full-matrix least-squares procedures to R = 0.054 and 0.040 for 1243 and 1272 reflections with I ≥ 1.5 and 3σ(I), respectively. The crystal structures are isomorphous and both feature six-membered B—(N—N)2—Ga rings having highly asymmetric boat conformations, unlike those observed for the majority of the homobinuclear analogs previously reported. The mean Ga—N and B—N distances in the two compounds are 1.977 and 1.61 Å. Keywords: pyrazagaboles, pyrazolyl-bridged heterocycles, crystal structures, synthesis of pyrazagaboles.

Synthesis and characterization of molybdenum–tin complexes derived from the molybdenum tricarbonyl anion, [MeGapz3]Mo(CO)3−, and organotin chlorides. X-ray crystal structure of [MeGapz3]Mo(CO)3SnPh3 (where pz = pyrazolyl, N2C3H3)

1986 ◽  
Vol 64 (2) ◽  
pp. 321-327 ◽  
Author(s):  
Emmanuel C. Onyiriuka ◽  
Steven J. Rettig ◽  
Alan Storr
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Heavy Atom ◽  
Synthesis And Characterization ◽  
Full Matrix ◽  
X Ray ◽  
Tin Complexes ◽  
Interesting Solution ◽  
Single Bonds

The reaction of the molybdenum tricarbonyl anion, [MeGapz3]Mo(CO)3−, with the organotin chlorides, Ph3SnCl, Me3SnCl, and Me2SnCl2, has yielded a series of complexes in which direct Mo—Sn single bonds are featured. The [MeGapz3]Mo(CO)3SnMe2Cl complex shows an interesting solution behavior in which a transition from a 3:4, or piano stool structure, to a 3:3:1, or capped octahedral arrangement, is thought to occur. The 3:3:1 structure has been demonstrated in the solid state for the [MeGapz3]Mo(CO)3SnPh3 compound by means of a crystal structure determination. Crystals of [methyltris(1-pyrazolyl)gallato-N,N,N](triphenylstannyl)tricarbonylmolybdenum are monoclinic, a = 11.4439(8), b = 19.5116(8), c = 15.2686(12) Å β = 111.370(3)°, Z = 4, space group P21/c. The structure was solved by conventional heavy-atom methods and was refined by full-matrix least-squares procedures to R = 0.025 and Rw = 0.031 for 5259 reflections with I ≥ 3σ(I). Important bond lengths include: Mo—Sn = 2.8579(3), Mo—N = 2.239(2)–2.244(2), Mo—C = 1.967(3)–2.000(3), Sn—C = 2.151(3)–2.166(3), Ga—N = 1.920(3)–1.931(3), and Ga—C = 1.943(4) Å.

Preparation and characterization of the osmium cluster complexes H2Os3(CO)8L(EtFcPCMe) (L = CO or PEt2Fc) and H2Os3(CO)8[(η-C5H3PEt2)Fe(η-C5H4)]

1993 ◽  
Vol 71 (3) ◽  
pp. 399-409 ◽  
Author(s):  
William R. Cullen ◽  
Steven J. Rettig ◽  
Tu Cai Zheng
Keyword(s):  
Least Squares ◽  
Heavy Atom ◽  
Molar Ratio ◽  
Asymmetric Unit ◽  
Full Matrix ◽  
Space Group ◽  
Cluster Complexes ◽  
Unit Space

Thermolysis of Os3(CO)11(PEt2Fc) (Fc = (η-C5H4)Fe(η-C5H5)) in octane for 8 h affords H2Os3(CO)9(EtFcPCMe), 10, and H2Os3(CO)8[(η-C5H3PEt2)Fe(η-C5H4)], 9e, in 15 and 65% yield, respectively. Heating Os3(CO)12 and PEt2Fc in 1:2 molar ratio in xylene for 10 h gives two isomers of H2Os3(CO)8(PEt2Fc)(EtFcPCMe), 11, in about 40% yield. Two crystalline modifications of the complex 9e have been obtained from the same solvent: 9eA, triclinic, a = 15.653(1), b = 15.799(1), c = 11.257(1) Å, α = 90.388(7)°, β = 109.740(6)°, γ = 82.445(6)°, Z = 4 (two molecules per asymmetric unit), space group [Formula: see text]; and 9eB, monoclinic, a = 9.889(2), b = 13.632(3), c = 18.927(4) Å, β = 97.36(2)°, Z = 4, space group P21/n. The structures were solved by heavy atom methods and were refined by full-matrix least-squares procedures to R = 0.033 and 0.037 for 8131 and 5145 reflections with I ≥ 3σ(I), respectively.

Reactions of nitriles with binuclear rhodium hydrides. The stepwise reduction of a carbon–nitrogen triple bond at two metal centres

1992 ◽  
Vol 70 (9) ◽  
pp. 2381-2389 ◽  
Author(s):  
Michael D. Fryzuk ◽  
Warren E. Piers ◽  
Steven J. Rettig
Keyword(s):  
Least Squares ◽  
Triple Bond ◽  
Heavy Atom ◽  
Full Matrix ◽  
Space Group ◽  
X Ray ◽  
Hydride Complexes ◽  
Stepwise Reduction ◽  
Rhodium Hydrides

The reaction of simple nitriles, R′CN (R′ = CH3, Ph, o-tol) with the electron-rich binuclear rhodium hydride derivatives [(R2PCH2CH2PR2)Rh]2(μ-H)2 (R = Pri: [(dippe) Rh]2(μ-H)2; R = OPri: [(dipope)Rh]2(μ-H)2) results in the formation of alkylideneimido derivatives [(R2PCH2CH2PR2)Rh]2(μ-H)(μ-N=CHR′), apparently by insertion of the nitrile moiety into a bridging hydride bond; this was confirmed by the reaction of nitriles with the dideuteride [(dippe)Rh]2(μ-D)2, which resulted in the formation of [(dippe)Rh]2(μ-D)(μ-N=CHR′). Further reduction can take place by addition of H2 to generate the corresponding amide hydride derivatives [(dippe)Rh]2(μ-H)(μ-NHCH2R′); this represents an overall stoichiometric reduction of a nitrile to a coordinated amide at a binuclear centre. These same amido-hydride complexes can be accessed by addition of amine to the starting binuclear rhodium hydride derivatives. The X-ray structure of [(Pri2PCH2CH2PPri2)Rh]2(μ-H)(μ-N=CHCH3) was undertaken to confirm the structure of these particular intermediates. Crystals of this material are monoclinic, a = 19.036(2), b = 15.139(1), c = 13.604(1) Å, β = 104.119(7)°, Z = 4, space group P21/c. The structure was solved by heavy atom methods and was refined by full-matrix least-squares procedures to R = 0.038 and Rw = 0.041 for 5814 reflections with I ≥ 3σ(I).

Crystal structures of o-phenylenediarsine oxychloride (a redetermination) and o-phenylenediarsine oxybromide

1975 ◽  
Vol 28 (1) ◽  
pp. 15 ◽  
Author(s):  
JC Dewan ◽  
K Henrick ◽  
AH White ◽  
SB Wild
Keyword(s):  
Least Squares ◽  
Crystal Structures ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Full Matrix ◽  
Space Group ◽  
X Ray ◽  
Limits Of Error

The crystal structures of the title compounds have been established by X-ray diffraction at 295 K, being refined by full-matrix least-squares to residuals of 0.054 (0.051) respectively 2715 (469) reflections with I > σ(I)]. Crystals are monoclinic, space group C2/c, the compounds being isomorphous. Oxychloride: a = 14.534(4), b = 8.337(2), c = 7.653(1)Ǻ, β = 106.48(1)�. Oxybromide: a = 14.884(4), b = 8.360(2), c = 7.726(1)Ǻ, β = 105.30(1)�, Z = 4. With the exception-of the arsenic- halogen distance, the geometries of the two molecules are identical within the limits of error: for the oxychloride As-O-As, 121.8(3); Cl- As-O,98.03(6); Cl-As-C, 97.2(2); O-As-C, 92. 9(2)� ; As-O, 1.787(3); As-C, 1.941(5) Ǻ. As-Cl is 2.222(2) and As-Br 2.381(2) Ǻ.

Molybdenum–tin and molybdenum–copper complexes derived from the molybdenum tricarbonyl anions, LMo(CO)3− (where L = HBpz3 or HBpz″3; pz = pyrazolyl, N2C3H3; and pz″ = 3,5-dimethylpyrazolyl, N2C5H7)

1988 ◽  
Vol 66 (8) ◽  
pp. 1997-2006 ◽  
Author(s):  
Yan-Yun Liu ◽  
Arthur Mar ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Least Squares ◽  
Copper Complex ◽  
Copper Complexes ◽  
Heavy Atom ◽  
Carbonyl Ligand ◽  
Octahedral Structure ◽  
Full Matrix ◽  
Space Group ◽  
Carbonyl Ligands

The pyrazolylborate molybdenum tricarbonyl anions, (HBpz3)Mo(CO)3− and (HBpz″3)Mo(CO)3−, have been utilized to prepare a number of heteronuclear bimetallic species containing Mo—Sn and Mo—Cu bonds. Crystals of [hydrotris(1-pyrazolyl)borato-N,N,N](triphenylstannyl)tricarbonylmolybdenum are monoclinic, a = 17.570(2), b = 14.077(2), c = 12.180(1) Å, β = 96.985(8)°, Z = 4, space group P21/n, those of [hydrotris(1-3,5-dimethylpyrazolyl)borato-N,N,N](chlorodimethylstannyl)tricarbonylmolybdenum are monoclinic, a = 11.044(3), b = 12.061(2), c = 20.218(4) Å, β = 100.43(1)°, Z = 4, space group P21/c, and those of [hydrotris(1-pyrazolyl)borato-N,N,N]tricarbonylmolybdenum(N,N,N′,N′-tetramethylethylenediamine)copper dichloromethane solvate are orthorhombic, a = 19.027(2), b = 16.995(2), c = 16.136(2) Å, Z = 8, space group Pbca. The structures were solved by conventional heavy atom methods and refined by full-matrix least-squares procedures to R = 0.044, 0.042, and 0.059 for 2084, 2502, and 1891 reflections, respectively. The two tin structures have a 3:3:1 capped octahedral structure with Mo—Sn bonds of 2.864(1) and 2.823(1) Å. The copper complex has a 3:4 piano stool arrangement of ligands about Mo with a Mo—Cu bond of 2.639(2) Å, two semibridging carbonyl ligands, and one terminal carbonyl ligand.

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.

Distorted chiolite crystal structures of α-Na5M3F14 (M=Cr,Fe,Ga) studied by X-ray powder diffraction

2003 ◽  
Vol 18 (2) ◽  
pp. 128-134 ◽  
Author(s):  
A. Le Bail ◽  
A.-M. Mercier
Keyword(s):  
Crystal Structures ◽  
Powder Diffraction ◽  
Room Temperature ◽  
Rietveld Refinements ◽  
Space Group ◽  
X Ray ◽  
Precise Characterization

The crystal structures of the chiolite-related room temperature phases α-Na5M3F14 (MIII=Cr,Fe,Ga) are determined. For all of them, the space group is P21/n, Z=2; a=10.5096(3) Å, b=7.2253(2) Å, c=7.2713(2) Å, β=90.6753(7)° (M=Cr); a=10.4342(7) Å, b=7.3418(6) Å, c=7.4023(6) Å, β=90.799(5)° (M=Fe), and a=10.4052(1) Å, b=7.2251(1) Å, c=7.2689(1), β=90.6640(4)° (M=Ga). Rietveld refinements produce final RF factors 0.036, 0.033, and 0.035, and RWP factors, 0.125, 0.116, and 0.096, for MIII=Cr, Fe, and Ga, respectively. The MF6 polyhedra in the defective isolated perovskite-like layers deviate very few from perfect octahedra. Subtle octahedra tiltings lead to the symmetry decrease from the P4/mnc space group adopted by the Na5Al3F14 chiolite aristotype to the P21/n space group adopted by the title series. Facile twinning precluded till now the precise characterization of these compounds.

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