Enantiomeric disorder in racemic cis-­dichlorobis(pentane-2,4-dionato)­titanium(IV)

The title compound, [Ti(C₅H₇O₂)₂Cl₂], adopts the cis configuration. The racemic compound crystallizes in space group P and each molecular site has 0.50 occupancy by each of the two enantiomorphs. The enantiomeric disorder is correlated in two dimensions.     

The optical resolution of tris(pentane-2,4-dionato)metal(III) complexes

A facile large-scale optical resolution of neutral [M(pd)₃] complexes, M = Cr(III), Co(III), Ru(III), Rh(III) and Ir(III), through enantioselective complex formation with (2R, 3R)-(-)-dibenzoyltartaric acid, is described.     

Diversity of supramolecular aggregation in copper(II) pentane-2,4-dionato compounds with methyl substituted 2-aminopyridines

Three copper(II) bis(pentane-2,4-dionato-κ ² O,O′) compounds with 2-amino-3-methylpyridine (2,3-ampy) (1), 2-amino-5-methylpyridine (2,5-ampy) (2), and 2-amino-4-methylpyridine (2,4-ampy) (3) were prepared by reaction of bis(pentane-2,4-dionato-κ ² O,O′)copper(II) with selected methyl substituted 2-aminopyridines. The coordination of Cu(II) in all three compounds is square pyramidal and intramolecular N–H?···?O hydrogen-bonding is present. X-ray crystallographic studies reveal different crystal aggregation influenced by a methyl substituent on pyridine. No intermolecular N–H?···?O hydrogen-bonding is present in 1. Intermolecular N–H?···?O hydrogen-bonding in 2 forms infinite chains and dimers are formed in 3. Extended 3-D aggregation was found in 2 via π–π and C–H?···?π (arene) interactions, while only chain formation was found in 1 and 3.     

The twisting power of some chiral tris-(pentane-2,4-dionato)metal(III) complexes in nematic liquid crystals

The twisting power (β) of tris(pentane-2,4-dionato)metal(III) complexes was measured in different nematic liquid crystals at variable temperature. Th     

Characterization of technetium-99m complexes of pentane-2,4-dione bis(N-methylthiosemicarbazone)

Further characterization of the two neutral technetium-99m (99mTc) complexes of pentane-2,4-dione bis-(N-methylthiosemicarbazone) (PETS) was carried out using a new dianionic PETS derivative, 3,3-dimethyl-pentane-2,4-dione bis(N-methylthiosemicarbazone) (DM-PETS), and the well characterized 99mTc complex of 2,2,9,9-tetramethyl-4,7-diaza-1,10-decanedithiol (DADT) as references. While PETS generated two neutral 99mTc complexes, 99mTc-PETS-L1 and 99mTc-PETS-L2, by both the stannous reduction method and the ligand exchange reaction with six-coordinated 99mTc(V) complex of N,N'-ethylenebis(acetylacetone imine), DM-PETS formed only one neutral 99mTc complex. 99mTc-PETS-L2, the more lipophilic complex of the two 99mTc-PETS, was obtained with a much higher yield than 99mTc-PETS-L1 by the ligand exchange reaction of PETS with the five-coordinated 99mTc(V) complex of glucoheptonate. In addition, while 99mTc-PETS-L2 and 99mTc-DADT remained unchanged in the presence of CN- anions, a breakdown of the original complexes was observed in 99mTc-PETS-L1 and 99mTc-DM-PETS. All four 99mTc complexes exhibited similar brain, heart and pancreas extraction when injected into mice. These cumulative results imply that 99mTc-PETS-L1 and 99mTc-DM-PETS are six-coordinated mononuclear 99mTc(V) complexes and that 99mTc-PETS-L2 is a five-coordinated mononuclear 99mTc(V) complex. These results also suggest that while the chelate ring structure of the 99mTc-dithiosemicarbazone (DTS) chelate played a significant role in its stability, ionization of the third proton of the PETS molecule and the subsequent resonating structure afforded further stability to the 99mTc-PETS complex. Markedly high lipophilicity of the 99mTc-PETS-L2 may also be explained by assuming that 99mTc-PETS-L2 is the five-coordinated resonating structure.     

Structure and properties of the volatile isomers of bis(1,1,1-trifluoro-5,5-dimethylhexane-2,4-dionato) of platinum(II)

In the work, isomeric complexes of platinum(II) with the (ptac)^–1 pivaloyltrifluoroacetonate ion (Pt((CH₃)₃–CO–CH–CO–CF₃)₂) are studied. The synthesis and chromatographic separation of Pt(ptac)₂ isomers are described, TGA data for the separated isomers are given, and the crystal structures of the solid phases are studied. The cis-Pt(ptac)₂ complex crystallizes in the space group P-1, a = 10.7091(4) Å, b = 12.7787(6) Å, c = 16.0154(8) Å, α = 92.389(2)°, β = 90.868(2)°, γ = 112.1260(10)°, V = 2027.39(16) ų, Z = 4, d _calc = 1.918 g/cm³. The trans-Pt(ptac)₂ complex crystallizes in the space group C2/m, a = 13.3235(5) Å, b = 8.5515(3) Å, c = 9.6694(3) Å, β = 118.5880(10)°, V = 967.38(6) Å3, Z = 2, d _calc = 2.010 g/cm3. The structures of the complexes are molecular, the Pt atom has a square coordination of four oxygen atoms of two ligands; for cis-Pt(ptac)2, the Pt–Oav distance is 1.968 Å, for trans-Pt(ptac)2 it is 1.980 Å.     

Association of tris(pentane-2,4-dionato)chromium(III) with modifiers of hydrogen-bond donors in supercritical carbon dioxide.

The solubility of tris(pentane-2,4-dionato)chromium(III) (Cr(acac)(3)) in supercritical carbon dioxide (SC-CO(2)) containing organic modifiers (1,1,1,3,3,3-hexafluoro-2-propanol (HFP) and 3,5-bis(trifluoromethyl)phenol (BTMP)) of hydrogen-bond donors was investigated by UV/VIS spectrophotometry. A great solubility enhancement of Cr(acac)(3) in SC-CO(2) was accomplished by adding HFP and BTMP. The association constant of Cr(acac)(3) with HFP and BTMP in SC-CO(2) could be determined from the relationship of the solubility enhancement against the concentration of the modifier. The association constant linearly increases with an increase in the acid dissociation constant of the modifiers.     

Hydrogen-bonding in ethanol adducts to bis(3-R-penta-2,4-dionato)nickel(II) species

Ethanol adducts of bis(3-R-penta-2,4-dionato) nickel(II) have been prepared by recrystallization of the corresponding nickel bisacetylacetonate species from ethanol, and their crystal structures have been determined by X-ray diffraction: R = methyl, C16H30NiO6, a = 5.177(1), b = 9.326(1), c = 9.649(1), a = 95.39(1), beta = 100.04(1), gamma = 97.16(1), space group Ponebar, Z = 1; R = hex-5-enyl, C26H46NiO6, a = 5.176(1), b = 9.677(1), c = 14.458(1), a = 92.333(3), beta = 93.945(4), gamma = 96.011(6), space group Ponebar, Z = 1; R = phenyl, C26H34NiO6, a = 27.399(1), b = 5.349(1), c = 19.827(2), beta = 117.410(7), space group C2/c, Z = 4. The compounds show remarkable differences in their ability to form hydrogen bonds in the solid phase and in solution, depending upon the nature of the substituent in the 3-position of the acetylacetone fragment. Analysis of the strength of hydrogen bonds within the limits of supermolecular approximation based on the results of calculations by DFT method has been carried out and were found to correlate with experimental observations.     

Different coordination modes and supramolecular aggregations in copper(II) pentane-2,4-dionato compounds with 2-pyridone and 3-hydroxypyridine

Abstract  

Copper(II) bis(pentane-2,4-dionato-κ² O,O′) compounds with 2-pyridone (1) and 3-hydroxypyridine (2) were prepared by the reaction of bis(pentane-2,4-dionato-κ² O,O′)copper(II) with selected ligands. The coordination of Cu(II) in both compounds is square pyramidal with the fifth coordination site occupied by the carbonyl oxygen atom of the 2-pyridone ligand in 1 and by the nitrogen atom of 3-hydroxypyridine in 2. The X-ray crystallographic studies revealed different crystal aggregation influenced by the ability of the 2-pyridone ligand to act as a hydrogen bond donor and acceptor, and 3-hydroxypyridine acting only as a hydrogen bond donor. Intermolecular N–H···O hydrogen bonding forms dimers in 1 and infinite chains in 2. Three-dimensional aggregation is achieved by π–π interactions and C–H···π (arene) hydrogen bonding.     

Kinetics of formation and dissociation of the ternary complex ion (pentane-2,4-dionato)(nitrilotriacetato)chromate(III) in aqueous media

Synthesis of solid [Cr(nta)(H₂O)₂] 1, kinetics and equilibrium of ots reaction with pentane-2,4-dione (Hpd) to form [Cr(nta)(pd)]⁻ 2 (H₃nta is nitrilotriacetic acid), aquation of 2 into 1, and some related reactions have been described. Parallel proton-independent and inverse proton-dependent paths lead from 1 to 2. The [H⁺]⁻¹ path arises from metal assisted deprotonation of HE, the enol form of Hpd. Aquation of 2 into 1 involves [Cr(Hnta)(pd)(H₂O]⁺ 2H (Hnta is tridentate nta) in addition to 2. The nta comples 1 is considerably more labile and a weaker acid than [Cr(H₂O)₆]³⁺.     

Isotope selective infrared laser-induced unimolecular dissociation of dimeric bis (1,1,1.5,5,5-hexafluoropentane-2,4-dionato) dioxouranium (vi)

The uranium isotope selective gas phase decomposition of [UO₂ (hfacac)₂]₂ has been measured following absorption of infrared laser radiation by either of two strong absorption features near 10.6 μm These results show that isotopic selectivity can be attained with high yield at Ion laser fluence.