Synthesis, characterization, and reactivity of a ruthenium(II) N,N′,N″-tris(2-pyridyl)phosphine complex. X-ray analysis of RuCl2(PPh3)(Ppy3) (py = 2-pyridyl)

1996 ◽  
Vol 74 (11) ◽  
pp. 2064-2072 ◽  
Author(s):  
Richard P. Schutte ◽  
Steven J. Rettig ◽  
Brian R. James
Keyword(s):  
Crystal Structure ◽  
Least Squares ◽  
Key Words ◽  
Phosphorus Atom ◽  
Electron Donors ◽  
Full Matrix ◽  
Space Group ◽  
X Ray ◽  
Phosphine Complex

Reaction of RuCl2(PPh3)3 with Ppy3 (py = 2-pyridyl) in benzene produced the N,N′,N″-Ppy3 complex RuCl2(PPh3)(Ppy3) 1. Crystals of RuCl2(PPh3)(Ppy3)•2CH2Cl2 (C35H31Cl6N3P2Ru) are monoclinic, a = 17.269(2), b = 10.797(1), c = 20.604(1) Å, β = 107.461(6)°, Z = 4, space group P21/c. The structure was solved by the Patterson method and was refined by full-matrix least-squares procedures to R = 0.039 and Rw = 0.035 for 4184 reflections with I ≥ 3σ(I). Complex 1 reacts in MeOH or benzene with two-electron donors (L) to give the chloride-substituted, [RuCl(L)(PPh3)(Ppy3)]PF6, or the triphenylphosphine-substituted products, RuCl2(L)(Ppy3), (L = CO, MeCN, PhCN), respectively. [RuCl(MeOH)(PPh3)(Ppy3)]BPh4 was also isolated. The non-coordinated phosphorus atom in 1 was oxidized to form RuCl2(PPh3)(OPpy3). Key words: ruthenium, pyridylphosphines, crystal structure

Porphyrins incorporating heterocyclic N-oxides: (oxidopyridyl)porphyrins, porphyrin-N-oxides, and a tirapazamine-porphyrin conjugate

1999 ◽  
Vol 77 (2) ◽  
pp. 182-198 ◽  
Author(s):  
Jeffrey J Posakony ◽  
Russell C Pratt ◽  
Steven J Rettig ◽  
Brian R James ◽  
Kirsten A Skov
Keyword(s):  
Crystal Structure ◽  
Least Squares ◽  
Key Words ◽  
Direct Methods ◽  
Spectroscopic Methods ◽  
Full Matrix ◽  
Space Group ◽  
X Ray

Porphyrins containing one to four 4-pyridyl groups as meso-substituents were synthesized via a mixed aldehyde condensation, and then "N-oxidized" with m-chloroperbenzoic acid to produce five novel (oxidopyridyl) porphyrins and seven porphyrin-N-oxides, which were characterized by analysis and spectroscopic methods, especially NMR; an X-ray crystal structure of 5-(1-oxido-4-pyridyl)-10,15,20-triphenylporphyrin was also obtained. Crystals of (oxidopyridyl)triphenylporphyrin are tetragonal, a = b = 15.174(1), c = 13.709(1) Å, Z = 4, space group I2d. The structure was solved by direct methods and refined by full-matrix least-squares procedures to R = 0.031 (Rw = 0.026) for 685 reflections with I [Formula: see text] 3σ(I). Sulfonation of two of the (oxidopyridyl)porphyrins was achieved readily with no loss of oxygen from the oxidopyridyl groups. Tirapazamine (3-amino-1,2,4-benzotriazine-1,4-di-N-oxide) was treated with triphosgene to yield the previously reported 2H-[1,2,4]oxadiazolo[3,2-c][1,2,4]benzotriazin-2-one-5-oxide (1); this reacts like an isocyanate and with 5-(4-aminophenyl)-10,15,20-triphenylporphyrin yields a tirapazamine-porphyrin conjugate (2).Key words: porphyrin-N-oxides, (oxidopyridyl)porphyrins, tirapazamine.

Ring contraction of 4-substituted 2,6-dichlorophenols. The crystal structure of 2,2,4α,5α-Tetrachloro-1α,3α-dihydroxycyclopentane-1,4-carbolactone

1977 ◽  
Vol 30 (10) ◽  
pp. 2195 ◽  
Author(s):  
RM Christie ◽  
RW Rickards ◽  
KJ Schmalzl ◽  
D Taylor
Keyword(s):  
Crystal Structure ◽  
Least Squares ◽  
Direct Methods ◽  
Major Product ◽  
X Ray Diffraction ◽  
Ring Contraction ◽  
Full Matrix ◽  
Space Group ◽  
X Ray ◽  
Counter Data

Alkaline chlorination of the 4-alkyl-2,6-dichlorophenols (2b) and (2c) proceeds through ring contraction and halolactonization to form the 4α- alkyl-2,2,5α-trichloro-1α,3α-dihydroxycyclopentane-1,4-carbolactones (4b) and (4c). Under similar conditions, 2,4,6-trichlorophenol affords the analogous 2,2,4α,5α-tetrachloro-1α,3α-dihydroxycyclopentane-1,4- carbolactone (4a) in low yield, in addition to the Hantzsch acid (3a) as the major product. The acid (3a) upon further treatment undergoes chloro-lactonization to give the lactone (4a). The structures of the lactones (4b) and (4c) follow from spectroscopic comparison with (4a), the structure of which has been established by X-ray diffraction (C6H4Cl4O4 orthorhombic a 13.485(1), b 12.348(1), c 11.371(1) Ǻ, space group Pccn, Z 8, solved by direct methods and refined by block-diagonal and full-matrix least squares to R 0.031, Rw 0.043 for 1313 unique counter data with I/σ(I) ≥ 3.0).

scholarly journals The Crystal Structure of the [Pt(diethylenetriamine)Br]Br Complex

1975 ◽  
Vol 53 (8) ◽  
pp. 1139-1143 ◽  
Author(s):  
Robert Melanson ◽  
Joseph Hubert ◽  
F. D. Rochon
Keyword(s):  
Crystal Structure ◽  
Least Squares ◽  
Thermal Parameters ◽  
Platinum Atom ◽  
Molecular And Crystal Structure ◽  
X Ray Diffraction ◽  
Full Matrix ◽  
Space Group ◽  
X Ray ◽  
Cell Parameters

The molecular and crystal structure of the [Pt(dien)Br]Br complex (dien = diethylenetriamine) has been studied by X-ray diffraction. The compound belongs to the orthorhombic Pca21 space group and the cell parameters are: a = 14.211, b = 4.940, c = 13.450 Å, and Z = 4. The refinement of the positional and anisotropic thermal parameters, carried out by full matrix least squares calculations, converged to R = 0.039 and Rw = 0.036.The coordination around the platinum atom is planar. The crystal consists of alternate layers of [Pt(dien)Br]+ cations and Br− ions parallel to the ac plane.

Crystal structure of Tris(N,N-diethyldithiocarbamato)thallium(III)

1978 ◽  
Vol 31 (9) ◽  
pp. 1927 ◽  
Author(s):  
DL Kepert ◽  
CL Raston ◽  
NK Roberts ◽  
AH White
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Least Squares ◽  
Title Compound ◽  
Electron Pair ◽  
X Ray Diffraction ◽  
Full Matrix ◽  
Space Group ◽  
X Ray

The crystal structure of the title compound, [Tl(S2CNEt2)3], has been determined by single-crystal X-ray diffraction methods at 295 K and refined by full-matrix least squares to a residual of 0.050 for 2517 'observed' reflections. Crystals are monoclinic, with space group A2/a, a 14.789(7), b 10.428(4), c 18.207(9) Ǻ, β 118.11(4)°, Z 4, and are isostructural with those of the previously determined gallium and indium analogues, the molecule having 2 symmetry with <Tl-S> 2.666 Ǻ. As in the dimethyl/thallium analogue, the departure of the TlS6 core symmetry from 3 is large and is examined in terms of electron-pair repulsion theory.

Verfeinerung der Kristallstruktur eines basaltischen Magnesio-Hastingsites

1981 ◽  
Vol 156 (3-4) ◽  
Author(s):  
E. M. Walitzi ◽  
F. Walter
Keyword(s):  
Crystal Structure ◽  
Least Squares ◽  
Least Squares Method ◽  
Three Dimensional ◽  
Full Matrix ◽  
Space Group ◽  
X Ray

AbstractThe crystal structure of the basaltic clino-amphibole magnesio-hastingsite was refined from three-dimensional photographic X-ray data by a full matrix least-squares method in the space group

Routes to dicationic ruthenium(II) nitrile complexes containing chelating diphosphine ligands: X-ray analyses of Ru(dppb)(MeCN)42+ 2PF6−(dppb = Ph2P(CH2)4PPh2) and trans-RuCl2(MeCN)4

1995 ◽  
Vol 73 (7) ◽  
pp. 1084-1091 ◽  
Author(s):  
Deryn E. Fogg ◽  
Steven J. Rettig ◽  
Brian R. James
Keyword(s):  
Crystal Structure ◽  
Least Squares ◽  
Steric Effect ◽  
Diphosphine Ligands ◽  
Diphosphine Ligand ◽  
Full Matrix ◽  
Space Group ◽  
X Ray ◽  
Infrared Data

Routes to the Ru(PP)(RCN)42+ 2PF6− complexes (PP = Ph2P(CH2)4PPh2, dppb; R = Me, Ph) from the Ru(II) precursors Ru2Cl4(PP)2, and Ru2Cl4(PP)(PPh3) have been established. The X-ray crystal structure of the dppb-MeCN derivative (3) is described, and the steric effect of the diphosphine ligand is examined by comparison with the crystal structure of trans-RuCl2(MeCN)4 (5), which is also presented. Crystals of 3 are triclinic, a = 13.845(3), b = 14.419(2), c = 12.984(3) Å, α = 108.75(2)°, β = 116.40(1)°, γ = 68.58(1)°, and Z = 2, space group [Formula: see text] and those of 5 are orthorhombic, a = 13.058(2), b = 11.790(2), c = 8.562(1) Å, and Z = 4, space group Pbca. The structures were solved by the Patterson method and refined by full-matrix least-squares procedures to R = 0.039 and 0.024 (Rw = 0.046 and 0.028) for 9973 and 1131 reflections with I ≥ 3σ(I), respectively. Crystallographic and infrared data suggest that the nitrile ligands function solely as σ-donors in these ruthenium(II) complexes. Keywords: ruthenium, nitriles, diphosphine ligands.

Crystal Structure of Tetraethylammonium Bromopentacarbonyltungstate(0)

1995 ◽  
Vol 48 (5) ◽  
pp. 1045 ◽  
Author(s):  
T Whyte ◽  
GA Williams
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Least Squares ◽  
X Ray Diffraction ◽  
Full Matrix ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
R Value

The crystal structure of tetraethylammonium bromopentacarbonyltungstate (0), [NEt4] [W(CO)5Br], has been determined by single-crystal X-ray diffraction methods at 22�1°C. Crystals are tetragonal, space group P4/n, with a 9.206(2), c 10.484(2) Ǻ, and Z 2. Full-matrix least-squares refinement gave a final R value of 0.034 for 820 independent reflections. The [W(CO)5Br]- anion possesses exact C4v symmetry, with bond lengths W-Br 2.736(1), W-COtrans 1.93(1) and W-COcis 2.034(6) Ǻ.

The crystal structure of the methyl-bridged yttrium-aluminium complex, [(η-C5H5)2YMe2AlMe2]

1978 ◽  
Vol 31 (2) ◽  
pp. 411 ◽  
Author(s):  
GR Scollary
Keyword(s):  
Crystal Structure ◽  
Structural Analysis ◽  
Least Squares ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Full Matrix ◽  
Space Group ◽  
X Ray ◽  
Yttrium Aluminium

A structural analysis of [(η-C5H5)2YMe2AlMe2] has been carried out by X- ray diffraction. Crystals are orthorhombic, space group Pna21, a 17.969(6), b 7.988(4), c 10.870(4) Ǻ, Z 4. The structure has been refined by a full-matrix least-squares procedure to R 0.052 for 663 observed reflections (Mo Kα automatic diffractometry). The structure contains a dimethyl bridge, the average bridging bond distances being 2.58(3) Ǻ for Y-C and 2.10(2) Ǻ for Al-C, and the Y-Al separation is 3.056(6) Ǻ.

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.

The crystal structure and stereochemistry of 2-acetyl-3,5,6-trihydroxy-5,6-dimethyl-2-cyclohexenones

1988 ◽  
Vol 66 (2) ◽  
pp. 246-248 ◽  
Author(s):  
Giorgio Adembri ◽  
Mirella Scotton ◽  
Alessandro Sega
Keyword(s):  
Crystal Structure ◽  
Least Squares ◽  
Structure Analysis ◽  
Direct Methods ◽  
Crystal Structure Analysis ◽  
Full Matrix ◽  
Space Group ◽  
X Ray ◽  
Bicyclic System ◽  
Centrosymmetric Dimers

The stereochemistry of 3a, one of the 2-acetyl-3,5,6-trihydroxy-5,6-dimethylcyclohexenones, obtained by rearrangement of 2,3-diacetyl-4-hydroxy-4-methylcyclopentenone, 2a, under basic conditions, was determined by an X-ray crystal structure analysis. An ORTEP plot shows the configuration of (5RS,6RS)-2-acetyl-3,5,6-trihydroxy-5,6-dimethylcyclohexenone and the presence of a conjugated chelated system involving the H-bonding between O(3)… H(31) and H(31)… O(2).Crystals of 3a are triclinic, a = 10.979(4), b = 7.766(3), c = 6.382(3) Å, α = 86.23(2), β = 72.86(1), γ = 88.23(2)°, Z = 2, space group [Formula: see text]. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.036 and Rw = 0.039 for 1324 reflections with I > 3σ(I).The structure of 3a consists of centrosymmetric dimers which contain a nearly planar bicyclic system of a cyclohexenone moiety and a chelated system (Scheme 2).The pathway of the reaction allows one to put forward some hypothesis on the stereochemistry of some analogues of the cyclohexenones 3a and 3b.Faisant appel à la diffraction des rayons-X, on a déterminé la stéréochimie du composé 3a, une des acétyl-2 trihydroxy-3,5,6 diméthyl-5,6 cyclohexénones obtenues par une transposition de la diacétyl-2,3 hydroxy-4 méthyl-4 cyclopenténone, 2a, en milieu alcalin. Une courbe ORTEP démontre que la configuration est (5RS,6RS) pour l'acétyl-2 trihydroxy-3,5,6 diméthyl-5,6 cyclohexénone et qu'il existe un système de chélation conjugué impliquant des liaisons hydrogènes entre O(3)… H(31) et H(31)… O(2).

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