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 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 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.

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.

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.

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).

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.

Complexes of the dimethylgallium-1-pyrazolyl-o-aminophenolato ligand, [Me2Ga(pz)(o-NH2C6H4O)]−. Formation and crystal structure of the molybdenum amidine complex, Mo(CO)2Br(η3-C3H5)[η2-HN=CMe(pz)] (where pz = pyrazolyl, N2C3H3)

1987 ◽  
Vol 65 (10) ◽  
pp. 2469-2477 ◽  
Author(s):  
G. D. Gracey ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Crystal Structure ◽  
Physical Properties ◽  
Least Squares ◽  
Heavy Atom ◽  
Full Matrix ◽  
Space Group ◽  
Benzene Solvate

The synthesis, characterization, and structures of complexes containing the o-aminophenolato ligand are detailed. A novel molybdenum amidine complex is also described. Crystals of (o-aminophenolato)dimethylgallium are monoclinic, a = 10.1970(9), b = 9.7597(7), c = 18.778(2) Å, β = 100.810(7)°, Z = 8, space group C2/c, those of bis(dimethylgallium-1-pyrazolyl-o-aminophenolato)nickel(II) benzene solvate are monoclinic, a = 20.491(1), b = 11.789(1), c = 15.789(1) Å, β = 103.413(7)°, Z = 4, space group C2/c, and those of η3-allyl(bromo)[2-(1-pyrazolyl)ethylidenarnino]dicarbonylmolybdenum(II) are monoclinic, a = 11.0278(4), b = 8.4461(2), c = 15.3747(5) Å, β = 109.208(3)°, Z = 4, space group P21/c. The structures were solved by conventional heavy atom methods and refined by full-matrix least-squares procedures to R = 0.030, 0.053, and 0.038 for 1980, 1684, and 1901 reflections, respectively. Reaction of the [Me2Ga(pz)(OC6H4NH2)]− ligand, L−, with [Re(CO)4Cl]2 results in the formation of LRe(CO)3 whose physical properties indicate a fac arrangement of the organogallate ligand.

Synthesis and structural characterization of bis(tropolonatodimethylgallium), [(C7H5O2)Ga(CH3)2]2

1984 ◽  
Vol 62 (9) ◽  
pp. 1705-1708 ◽  
Author(s):  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Solid State ◽  
Physical Properties ◽  
Least Squares ◽  
Structural Characterization ◽  
Heavy Atom ◽  
Coordination Geometry ◽  
State Structure ◽  
Full Matrix ◽  
Trigonal Bipyramidal

Details of the synthesis, physical properties, and solid-state structure of [(C7H5O2)Ga(CH3)2]2 are reported. Crystals of bis(tropolonatodimethylgallium) are monoclinic, a = 10.2669(9), b = 9.3237(3), c = 10.8671(10) Å, β = 112.896(4)°, Z = 2, space group P21/n (22°C, λ = 0.70930 Å). The structure was solved by conventional heavy-atom techniques and was refined by full-matrix least-squares procedures to R = 0.034 and Rw = 0.037 for 1746 reflections with I ≥ 3σ(I). The centrosymmetric binuclear dimer features five-coordinate gallium atoms having irregular trigonal bipyramidal coordination geometry and a planar four-membered Ga2O2 ring. Important bond lengths (corrected for libration) are Ga—O(equatorial) = 1.972(2), Ga—O(axial) = 2.025(2) and 2.551(2) Å, and Ga—C = 1.951(4) and 1.954(4) Å.

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.

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