Solid-state reactions of organometallic aldehydes with optically active primary β-hydroxyamines

The solid-state reactions of crystalline ferrocenyl- and ruthenocenylaldehydes with optically active primary β-hydroxyamines were studied at ∼20 °C. The yield of the products increases substantially in the presence of K₂CO₃. The tautomeric equilibrium between imines and diastereomeric oxazolidines with the predominant formation of one of them is established in solutions of the products in CDCl₃. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2240–2243, December, 1997.     

Chiral modification of polyformyl compounds of dendrite type with optically active primary and secondary 1,2-aminoalcohols

Procedures were developed for preparation of optically active dendrones and dendrimers with terminal 1,2-hydroxylimino, 1,2-hydroxylamino and oxazolidinyl groups containing ether bonds in the branches and ester bonds in the backbone of the macromolecule. The compounds described may serve as chiral ligands for asymmetric metallocomplex catclysis.     

The solid-state interaction of organometallic aldehydes with 1,8-naphthylenediamine

Organometallic derivatives of 2,3-dihydroperimidine were obtained by the solid state interaction of ferrocene-, cymantrene-, and ruthenocenecarbaldehydes with 1,8-naphthylenediamine. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya. No. 1, pp. 145–146, January, 2000.     

PRESSURE-VELOCITY EQUILIBRIUM HYDRODYNAMIC MODELS

This article describes mathematical models for phase separated mixtures of materials that are in pressure and velocity equilibrium but not necessarily temperature equilibrium. General conditions for constitutive models for such mixtures that exhibit a single mixture sound speed are discussed and specific examples are described.     

Metal-free and transition-metal tetraferrocenylporphyrins part 1: synthesis, characterization, electronic structure, and conformational flexibility of neutral compounds

H(2)TFcP [TFcP = 5,10,15,20-tetraferrocenyl porphyrin(2-)] was prepared by a direct tetramerization reaction between pyrrole and ferrocene carbaldehyde in the presence of a BF(3) catalyst, while the series of MTFcP (M = Zn, Ni, Co and Cu) were prepared by a metallation reaction between H(2)TFcP and respective metal acetates. All compounds were characterized by UV-vis and MCD spectroscopy, APCI MS and MS/MS methods, high-resolution ESI MS and XPS spectroscopy. Diamagnetic compounds were additionally characterized using (1)H and (13)C NMR methods, while the presence of low-spin iron(ii) centers in the neutral compounds was confirmed by M?ssbauer spectroscopy and by analysis of the XPS Fe 2p peaks, revealing equivalent Fe sites. XPS additionally showed the influence on Fe 2p binding energies exerted by the distinct central metal ions. The conformational flexibility of ferrocene substituents in H(2)TFcP and MTFcP, was confirmed using variable-temperature NMR and computational methods. Density functional theory predicts that alpha,beta,alpha,beta atropisomers with ruffled porphyrin cores represent minima on the potential energy surfaces of both H(2)TFcP and MTFcP. The degree of non-planarity is central-metal dependent and follows the trend: ZnTFcP < H(2)TFcP approximately CuTFcP < CoTFcP < NiTFcP. In all cases, a set of occupied, predominantly ferrocene-based molecular orbitals were found between the highest occupied and the lowest unoccupied, predominantly porphyrin-based molecular orbitals. The vertical excitation energies of H(2)TFcP were calculated at the TDDFT level and confirm the presence of numerous predominantly metal-to-ligand charge-transfer bands coupled via configurational interaction with expected intra-ligand pi-pi* transitions.     

Novel planar chiral phosphite: Preparation and use in the synthesis of Pd(II) complexes and in Pd-catalyzed allylic alkylation

The planar chiral diaryl phosphorimidite ligand containing additional C-stereocenters and neutral and cationic palladium(II) chelates with this ligand, cis-[Pd(η²-P,N)Cl₂] and [Pd(Allyl)(η²-P,N)]BF₄, were synthesized for the first time. The possibility of using these compounds in asymmetric allylic alkylation of 1,3-diphenylallyl acetate with dimethyl malonate in an optical yield of up to 73% was demonstrated.     

The solid-state interaction of organometallic aldehydes with 1,8-naphthylenediamine

Organometallic derivatives of 2,3-dihydroperimidine were obtained by the solid state interaction of ferrocene-, cymantrene-, and ruthenocenecarbaldehydes with 1,8-naphthylenediamine. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya. No. 1, pp. 145–146, January, 2000.