Spectroscopic and kinetic study of the reaction of trans-nitrosylchlorobis(dimethylglyoximate)ruthenium(II) with acetone in the presence of amines

Summary The complex trans-[Ru(NO)(dmgH)₂Cl] (dmgH = dimethylglyoximate ion) reacts with Me₂CO in the presence of NH₃ or substituted amines such as MeNH₂ and 4-NH₂CH₂py (py = pyridine), to yield intermediate addition compounds of the general formula trans-[Ru(dmgH)₂Cl{N(OH)CHC(NHR)Me}]^-. The kinetic, analytical and spectroscopic (electronic, resonance Raman and i.r.) results are consistent with nucleophilic attack by enamines, e.g. CH₂=C(NHR)Me, on the coordinated NO⁺ ligand.     

Mixed ``Amide-phosphoryl' Calix[4]arenes. On the Selectivity of Two Conformers Towards Alkali Ion Complexation

The binding properties of cone-5,11,17,23-tetra-tert-butyl-25,27-bis(diethylcarbamoyl-methoxy)-26,28-bis(diphenylphosphinoylmethoxy)calix[4] arene (cone-1) towards alkali metals have beencompared with those of the corresponding partial-cone conformer (paco- 1). Bothhybrid ligands form stable complexes with alkalipicrates in tetrahydrofuran having a 1 : 1cation/ligand ratio. Regarding extractability, thatpresented by cone-1 decreases continuallyon-going from Li/Na to Cs, while that for paco-1 presents a peak selectivity for Na (withthe following order Na > K > Rb > Li > Cs).These selectivities parallel, respectively, resultsobtained for extraction and transport experiments. Thekinetics of the alkali metal thiocyanate transportthrough a bulk liquid membrane containing theseligands in 1,2-dichloroethane could be rationalised interms of a simple mathematical model. The lowertransfer coefficients found for paco-1 relative to cone-1 reflect the larger sizeof the diffusing paco-complex.