Selenosalicylate; a little-studied heavy-element analogue of the versatile thiosalicylate ligand.

Selenosalicylic acid (ortho-HSeC6H4CO2H), the heavy element congener of the widely studied thiosalicylic acid, was prepared by reaction of 2-carboxybenzenediazonium chloride (HO2CC6H4N2+Cl-) with Na2Se2, followed by reduction of the resulting diselenide (SeC6H4CO2H)2 with zinc and acetic acid. The coordination chemistry of the selenosalicylate ligand towards a variety of platinum(ii), palladium(ii), nickel(ii), gold(iii), gold(i), rhodium(iii), iridium(iii) and ruthenium(ii) centres was explored. X-ray crystal structure determinations were carried out on the complexes [Pt(SeC6H4CO2)(PPh3)2], [{(p-cym)Ru(SeC6H4CO2)}2] (p-cym = η6-p-cymene, CH3C6H4CH(CH3)2), [{Cp*Rh(SeC6H4CO2)}2] (Cp* = η5-C5Me5) and [Cp*Ir(SeC6H4CO2)(PPh3)], and comparisons are made with corresponding thiosalicylate complexes. The complexes were characterised by NMR spectroscopy as well as ESI mass spectrometry, which indicated a greater propensity for fragmentation including by selenium loss, compared to the thiosalicylate analogues. Hirshfeld surface analysis to visualise and quantify intermolecular interactions revealed the dominance of H⋯H contacts in [{(p-cym)Ru(SeC6H4CO2)}2] and [Cp*Ir(SeC6H4CO2)(PPh3)].

The Influence of the Halide in the Crystal Structures of 1-(2,3,5,6-Tetrafluoro-4-pyridyl)-3-benzylimidazolium Halides.

The crystal structures of 1-(2,3,5,6-tetrafluoro-4-pyridyl)-3-benzylimidazolium chloride (1) and iodide (3) have been determined by single crystal X-ray diffraction. The crystal structure of 1 is similar to that of the bromide salt (2), possessing anion···C5F5N···C6H5 motifs, whilst that of 3 contains columns of alternating iodide anions and parallel tetrafluoropyridyl rings. All three crystal structures possess C(1)−H∙∙∙X− and C(2)−H∙∙∙X− hydrogen bonding. DFT calculations reveal that the strengths of the hydrogen bonding interactions lie in the order C(1)−H···X− > C(3)−H···X− > C(2)−H···X− for the same halide (X−) and Cl− > Br− > I− for each position. It is suggested that salt 3 adopts a different structure to salts 1 and 2 because of the larger size of iodide.

Nucleophilic Fluorination Catalyzed by a Cyclometallated Rhodium Complex.

Quantitative catalytic nucleophilic fluorination of a range of acyl chlorides to acyl fluorides was promoted by a cyclometallated rhodium complex [(η5,κ2C-C5Me4CH2C6F5CH2NC3H2NMe)- RhCl] (1). 1 can be prepared in high yields from commercially available starting materials using a one-pot method. The catalyst could be separated, regenerated, and reused. Rapid quantitative fluorination generated the fluoride analogue of the active pharmaceutical ingredient probenecid. Infrared in situ monitoring verified the clean conversion of the substrates to products. VTNA graphical kinetic analysis and DFT calculations lead to a postulated reaction mechanism involving a nucleophilic Rh-F bond.

Theoretical Study of the Structures of 4-(2,3,5,6-Tetrafluoropyridyl)Diphenylphosphine Oxide and Tris(Pentafluorophenyl)Phosphine Oxide: Why Does the Crystal Structure of (Tetrafluoropyridyl)Diphenylphosphine Oxide Have Two Different P=O Bond Lengths?

The crystal structure of 4-(2,3,5,6-tetrafluoropyridyl)diphenylphosphine oxide (1) contains two independent molecules in the asymmetric unit. Although the molecules are virtually identical in all other aspects, the P=O bond distances differ by ca. 0.02 Å. In contrast, although tris(pentafluorophenyl)phosphine oxide (2) has a similar crystal structure, the P=O bond distances of the two independent molecules are identical. To investigate the reason for the difference, a density functional theory study was undertaken. Both structures comprise chains of molecules. The attraction between molecules of 1, which comprises lone pair-π, weak hydrogen bonding and C-H∙∙∙arene interactions, has energies of 70 and 71 kJ mol-1. The attraction between molecules of 2 comprises two lone pair-π interactions, and has energies of 99 and 100 kJ mol-1. There is weak hydrogen bonding between molecules of adjacent chains involving the oxygen atom of 1. For one molecule, this interaction is with a symmetry independent molecule, whereas for the other, it also occurs with a symmetry related molecule. This provides a reason for the difference in P=O distance. This interaction is not possible for 2, and so there is no difference between the P=O distances of 2.

Conversion of haloform to carbonate by iridium N-heterocyclic carbene complexes and silver(i) oxide.

The reaction between haloform, the complexes [Cp*IrCl2(κC-MeNC3H2NCH2Ar)] (Ar = C6H3F2-2,6, C6H3F-2-Cl-6, C6H3Me2-2,6) and silver(i) oxide proceeded by carbon-halogen bond fission to yield the carbonate complexes [Cp*Ir(κ2O-CO3)(κC-MeNC3H2NCH2Ar)].

Intramolecular Hydrogen Bonding in Substituted Aminoalcohols.

The qualifying features of a hydrogen bond can be contentious, particularly where the hydrogen bond is due to a constrained intramolecular interaction. Indeed there is disagreement within the literature whether it is even possible for an intramolecular hydrogen bond to form between functional groups on adjacent carbon atoms. This work considers the nature of the intramolecular interaction between the OH (donor) and NH2 (acceptor) groups of 2-aminoethanol, with varying substitution at the OH carbon. Gas-phase vibrational spectra of 1-amino-2-methyl-2-propanol (BMAE) and 1-amino-2,2-bis(trifluoromethyl)-2-ethanol (BFMAE) were recorded using Fourier transform infrared spectroscopy and compared to literature spectra of 2-aminoethanol (AE). Based on the experimental OH-stretching frequencies, the strength of the intramolecular hydrogen bond appears to increase from AE < BMAE ≪ BFMAE. Non-covalent interaction analysis shows evidence of an intramolecular hydrogen bond in all three molecules, with the order of the strength of interaction matching that of experiment. The experimental OH-stretching vibrational frequencies were found to correlate well with the calculated kinetic energy density, suggesting that this approach can be used to estimate the strength of an intramolecular hydrogen bond.

Minimizing side reactions in chemoenzymatic dynamic kinetic resolution: organometallic and material strategies.

Chemoenzymatic dynamic kinetic resolution (DKR) of rac-1-phenyl ethanol into R-1-phenylethanol acetate was investigated with emphasis on the minimization of side reactions. The organometallic hydrogen transfer (racemization) catalyst was varied, and this was observed to alter the rate and extent of oxidation of the alcohol to form ketone side products. The performance of highly active catalyst [(pentamethylcyclopentadienyl)IrCl(2)(1-benzyl,3-methyl-imidazol-2-ylidene)] was found to depend on the batch of lipase B used. The interaction between the bio- and chemo-catalysts was reduced by employing physical entrapment of the enzyme in silica using a sol-gel process. The nature of the gelation method was found to be important, with an alkaline method preferred, as an acidic method was found to initiate a further side reaction, the acid catalyzed dehydration of the secondary alcohol. The acidic gel was found to be a heterogeneous solid acid.

Enhanced adsorption of Cd (II) on a hydrous Al (III) floc in the presence of a modified form of polyethylenimine.

A polymer modified with succinic anhydride has been investigated for the adsorption of cadmium (II) on a freshly precipitated aluminium (III) hydroxide floc. The proportion of chelate attached to the polymer is varied to determine the relationship between carboxyl and amino groups on the polyelectrolyte, in terms of enhanced adsorption of cadmium (II) on a hydrous aluminium floc. The presence of polyelectrolyte enhanced the adsorption of 3.3 ppm Cd (II) on a 333 ppm Al (III) floc at every concentration of polyelectrolyte investigated. The proportion of succinic anhydride attached to the polymer had an impact on the increased adsorption of Cd (II) on an Al (III) floc observed. A decreasing proportion of succinic anhydride to polymer resulted in a decrease in the amount of cadmium adsorbed on the floc. Above pH 8, a decrease in the % Cd (II) adsorbed on the floc and % Al (III) retained within the floc decreases with the presence of polyelectrolyte as a result of the formation of soluble Cd-Polyethylenimine-succinic acid (PEISA) complexes. When the Al-PEISA combination was applied to a complex matrix where Cd (II), Cu (II) and Ni (II) ions competed for adsorption, enhanced adsorption was observed for Cd (II) and Ni (II). At pH 7, dissolution of the floc observed with the addition of discrete chelates was not observed with the addition of polyelectrolytes.