2,6-Dichloro-aniline-4-(2,6-dichloro-anilino)-pent-3-en-2-one (1/2).

The asymmetric unit of the title compound, C6H5Cl2N·2C11H11Cl2NO, is composed of one mol-ecule of an enamino-ketone [i.e. -(2,6-dichloro-phenyl-amino)-pent-3-en-2-one] and half a mol-ecule of 2,6-dichloro-aniline, the whole mol-ecule of the latter component being generated by twofold rotational symmetry.

Electronic influence of β-diketonato-type ligands on the coordination of 1,5-cyclooctadiene to palladium(II) as defined by 'Venus fly trap' geometric parameters.

A range of single-crystal structures of the type [Pd(cod)(LL'-Bid)]A, where LL'-Bid = acetylacetonato (acac), thenoyltrifluoroactetonato (thtfac) and hexafluoroacetylacetonato (hfacac), and A = tetrafluoroborate (BF(4)(-)) and hexafluorophosphate (PF(6)(-)), are reported. The complexes [Pd(cod)(acac)]PF(6) (I), [Pd(cod)(thtfac)]PF(6) (III), [Pd(cod)(thtfac)]BF(4) (IV) and [Pd(cod)(hfacac)]PF(6) (V) are isostructural in the monoclinic space group P2(1)/c. The influence of the variation of the β-diketonato-type ligands on the coordination geometry of cis,cis-1,5-cycloocta-1,5-diene (cod) was investigated and found that no significant changes to the Pd-C and C=C bond distances were observed.

4-(2-Chloro-phenyl-amino)-pent-3-en-2-one.

In the title compound, C(11)H(12)ClNO, intra-molecular N-H⋯O hydrogen bonding is present. The dihedral angle between the benzene ring and the pentenone unit is 46.52 (5)°.

4-(2,3-Dimethyl-anilino)pent-3-en-2-one.

In the title compound, C(13)H(17)NO, the dihedral angle between the aryl ring and the amino-acryl-aldehyde mean plane [N-C=C-C=O; maximum deviation = 0.0144 (9) Å] is 53.43 (4)°.

Dicarbon-yl[4-(2,6-dimethyl-phenyl-amino)-pent-3-en-2-onato-κ(2)N,O]rhodium(I).

In the title compound, [Rh(C(13)H(16)NO)(CO)(2)], a square-planar coordination geometry is observed around the Rh(I) atom, formed by the N and O atoms of the bidentate ligand and two C atoms from two carbonyl ligands. The Rh(I) atom is displaced from the plane through these surrounding atoms by 0.0085 (2) Å.

5-(Phenyl-diazen-yl)tropolone.

THE TITLE COMPOUND [SYSTEMATIC NAME: (E)-2-hy-droxy-5-(phenyl-diazen-yl)cyclo-hepta-2,4,6-trien-1-one], C(13)H(10)N(2)O(2), is essentially planar with an r.m.s.

4-(2,6-Dibromo-4-fluoro-anilino)pent-3-en-2-one.

The title enamino-ketone, C(11)H(10)Br(2)FNO, has a roughly planar pentenone chain; the maximum displacement of an atom from the pentenone plane is 0.071 (4) Å. The dihedral angle between the benzene ring and the pentenone unit is 77.

(2-Methyl-4-oxo-4H-pyran-3-olato-κO,O)bis-(triphenyl-phosphane-κP)copper(I)-triphenyl-phosphane-methanol (1/1/1).

In the title compound, [Cu(C(6)H(5)O(3))(C(18)H(15)P)(2)]·C(18)H(15)P·CH(3)OH, the pyran-4-one ring is appromimately planar (r.m.s deviation = 0.

Steric vs. electronic anomaly observed from iodomethane oxidative addition to tertiary phosphine modified rhodium(i) acetylacetonato complexes following progressive phenyl replacement by cyclohexyl [PR(3) = PPh(3), PPh(2)Cy, PPhCy(2) and PCy(3)].

Rhodium(i) acetylacetonato complexes of the formula [Rh(acac)(CO)(PR(3))] [acac = acetylacetonate, PR(3) = PPh(3) 1, PCyPh(2) 2, PCy(2)Ph 3, PCy(3) 4] were synthesized and the iodomethane oxidative addition to these complexes were studied. Spectroscopic and low temperature (100 K) single crystal X-ray crystallographic data of the rhodium complexes (1-4) indicate a systematic increase in both steric and electronic parameters of the phosphine ligands as phenyl groups on the tertiary phosphine are progressively replaced by cyclohexyl groups in the series. Second order rate constants for the alkyl formation in the oxidative addition of iodomethane in dichloromethane at 25 degrees C vary with approximately one order-of-magnitude from 6.

Bis[2-(methyl-amino)-troponato]copper(II).

In the title compound, [Cu(C(8)H(8)NO)(2)], a strictly square-planar geometry about the Cu(II) metal atom is observed. Substitution of an O atom with a methyl-functionalized N atom does not significantly alter the bond distances and angles in the copper(II) complex when compared with a similar bis-(troponato)copper(II) complex. π-π stacking is observed between the tropolone rings, with inter-planar distances of 3.

4-[(4-Methyl-phen-yl)amino]-pent-3-en-2-one.

The title enamino-ketone, C(12)H(15)NO, is a derivative of 4-(phenyl-amino)-pent-3-en-2-one with an approximately planar pentenone backbone, the greatest displacement from the plane being 0.042 (1) Å; the asymmetry in C-C distances in the group suggests the presence of unsaturated bonds. The dihedral angle between the benzene ring and the pentenone plane is 29.

4-(2-Methyl-anilino)pent-3-en-2-one.

The title enamino ketone, C(12)H(15)NO, a derivative of 4-(phenyl-amino)-pent-3-en-2-one, presents a roughly planar [greatest displacement of an atom from the pentenone plane is 0.033 (2) Å] pentenone backbone, enhanced by an intra-molecular N-H⋯O hydrogen bond; the asymmetry in C-C distances in the group suggests the presence of unsaturated bonds. The overall geometry in the free ligand differs significantly from that in other reported compounds, in which it is coordinated to rhodium; this is reflected in the bond distances [the N⋯O distance is significantly increased (0.

Formation and reactivity of [(tacn)-N-CO-Re(III)Br(CO)(2)](+) in water: a theoretical and experimental study.

The chemistry of [(tacn)-N-CO-Re(III)(CO)(2)Br]X (X = Cl or Br), obtained in good yield from the reaction of fac-[(tacn)Re(I)(CO)(3)]Br (1, tacn = 1,4,7-triazacyclononane) with X(2) in water, is described. The [(tacn)-N-CO-Re(III)(CO)(2)Br]X complex (2 with X = Br(-); 2a with X = BrCl(2)(-)), which we have previously communicated, is characterized by an unusual three-membered ring acyl amide bond. Complex 2 is stable as a solid but is reactive in aqueous solution.

Bis[tris-(4-fluoro-phen-yl)phosphine-κP](tropolonato-κO,O')copper(I).

The title compound, [Cu(C(7)H(5)O(2))(C(18)H(12)F(3)P)(2)], a copper(I) tris-(4-fluoro-phen-yl)phosphine tropolonate derivative, is the first tropolonate complex with fluorinated aryl-phosphine ligands. The Cu(I) atom has a distorted tetra-hedral coordination; the most important geometrical parameters of the mol-ecule are: Cu-P = 2.2377 (10) and 2.

Nitratotris(triphenyl-phosphine)copper(I) methanol solvate.

The title compound, [Cu(NO(3))(C(18)H(15)P)(3)]·CH(3)OH, is a methanol solvate derivative of nitratotris(triphenyl-phos-phine)copper(I). The complex crystallizes with three triphenyl-phosphine ligands coordinated to the copper centre, with an O-H⋯O hydrogen bond observed between the nitrate ligand and the methanol solvent mol-ecule. The coordination around the Cu(I) centre is distorted tetrahedral.

Bis(triphenyl-phosphine-κP)(tropolonato-κO,O')silver(I) dichloro-methane solvate.

The title compound, [Ag(C(7)H(5)O(2))(C(18)H(15)P)(2)]·CH(2)Cl(2), crystallizes with a distorted tetra-hedral geometry about the Ag(I) atom, defined by two O atoms from one tropolonate ligand and two P atoms from two triphenyl-phosphine ligands. It is an example of a new type of tropolone derivative that has not been characterized via solid-state methods.

Dibromidobis(triphenyl-arsine)palladium(II).

In the title compound, [PdBr(2)(C(18)H(15)As)(2)], the Pd(II) ion resides on a centre of symmetry and is coordinated by two As atoms [Pd-As = 2.4184 (3) Å] and two Br anions [Pd-Br = 2.4196 (3) Å] in a slightly distorted square-planar geometry [As-Pd-Br = 90.

Carbonyl[4-(2,6-dimethyl-phenyl-amino)pent-3-en-2-onato-κN,O](triphenyl-phosphine-κP)rhodium(I) acetone hemi-solvate.

In the title compound, [Rh(C(13)H(16)NO)(C(18)H(15)P)(CO)]·0.5C(3)H(6)O, the Rh atom exhibits a square-planar coordination geometry, being coordinated by the N and O atoms of the bidentate β-diketonato ligand, a P atom from the triphenyl-phosphine unit and a C atom from the carbonyl group. The asymmetric unit also contains a disordered half-mol-ecule, lying about an inversion center, of the acetone solvate.

trans-Dibromidobis[tris-(4-chloro-phen-yl)phosphine]palladium(II).

In the title compound, [PdBr(2)(C(18)H(12)Cl(3)P)(2)], the Pd(II) ion is situated on a centre of symmetry and is coordinated by two Br anions [Pd-Br = 2.4252 (2) Å] and two P-donor ligands [Pd-P = 2.3317 (6) Å] in a slightly distorted square-planar geometry [P-Pd-Br = 86.

trans-Dibromidobis[diphen-yl(p-tol-yl)phosphine]palladium(II).

In the title compound, [PdBr(2)(C(19)H(17)P)(2)], the Pd(II) ion resides on a centre of symmetry and is coordinated by two Br anions [Pd-Br = 2.4266 (2) Å] and two P-donor ligands [Pd-P = 2.3462 (5) Å] in a slightly distorted square-planar geometry [P-Pd-Br = 93.

trans-Dibromidobis(tri-p-tolyl-arsine)palladium(II).

In the title compound, [PdBr(2)(C(21)H(21)As)(2)], the Pd(II) ion, residing on a centre of symmetry, is coordinated by two As donor atoms [Pd-As = 2.4276 (2) Å] and two Br anions [Pd-Br = 2.4194 (2) Å] in a distorted square-planar geometry [Br-Pd-As = 87.

Carbon-yl[4-(2,3-dimethyl-phenyl-amino)pent-3-en-2-onato-κN,O](triphenyl-phosphine-κP)rhodium(I).

In the title compound, [Rh(C(13)H(16)NO)(C(18)H(15)P)(CO)], the coordination geometry of the Rh(I) atom is square-planar, formed by the coordinating N and O atoms of the bidentate enaminoketonate ligand, one C atom from the carbonyl group and a P atom from triphenyl-phosphine. The complex displays a 0.591 (3):0.

Tetra-kis(1,1,1-trifluoro-acetyl-acetonato-κO,O')zirconium(IV) toluene solvate.

In the title compound, [Zr(C(5)H(4)F(3)O(2))(4)]·C(7)H(8), the Zr atom is in a square-anti-prismatic coordination geometry that comprises four O,O'-bidentate trifluoro-acetyl-acetonate ligands. The O-Zr-O bite angles of the acetonate ligands range from 75.27 (5) to 75.

Quantitative computational thermochemistry of transition metal species.

The correlation consistent Composite Approach (ccCA), which has been shown to achieve chemical accuracy (+/-1 kcal mol-1) for a large benchmark set of main group and s-block metal compounds, is used to compute enthalpies of formation for a set of 17 3d transition metal species. The training set includes a variety of metals, ligands, and bonding types. Using the correlation consistent basis sets for the 3d transition metals, we find that gas-phase enthalpies of formation can be efficiently calculated for inorganic and organometallic molecules with ccCA.

Rhodium hydride formation in the presence of a bulky monophosphite ligand: a spectroscopic and solid-state investigation.

A study has been carried out on rhodium catalyst preforming when modified with the bulky tris(2,4-di-tert-butylphenyl) phosphite, P(Obtbp)(3). X-Ray crystal structure determinations of a tropolone-type precursor complex [Rh(TropBr(3))(CO){P(Obtbp)(3)}].P(Obtbp)(3).