Roman N. Naumov

Water-soluble aminomethyl(ferrocenylmethyl)phosphines and their trinuclear transition metal complexes

Abstract Reactions of bis(hydroxymethyl)ferrocenylmethylphosphine ( 1 ) with amino acids ( o -aminobenzoic acid, potassium glycinate and 5-aminoisophthalic acid) lead to the metal-containing phosphino amino acids 1,3-bis(carboxymethyl)-5-(ferrocenylmethyl)-1,3-diaza-5-phosphacyclohexane ( 2 ), bis( o -carboxyphenylaminomethyl)ferrocenylmethylphosphine ( 3 ), and 1,5-bis( meta -dicarboxyphenyl)-3,7-bis(ferrocenylmethyl)-1,5-diaza-3,7-diphosphacyclooctane ( 4 ), respectively. Water-soluble trinuclear complexes 5 and 6 were obtained by complexation of 4 with [MCl 2 (cod)] (M=Pt, Pd; cod=cyclooctadiene) in DMF. Compounds 1 – 6 were characterized by multinuclear NMR and IR spectroscopy and microanalysis.

Novel chiral 1,5-diaza-3,7-diphosphacyclooctane ligands and their transition metal complexes

Reaction of bis(hydroxymethyl)phenylphosphine with (R)- or (S)-α-methylbenzylamine leads to the novel cyclic chiral bisphosphine ligands 1,5-(R,R)- and 1,5-(S,S)-bis(α-methylbenzyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane (1r or 1s). Novel chiral chelate complexes of PtII (2r, 3r and 3s), PdII (4s, 5s) and ReI (6r) have been obtained by reaction of 1r or 1s with [MCl2(cod)] (M = Pt, Pd; cod = 1,5-cyclooctadiene) and [{ReBr(CO)3(thf)}2]. Compounds 1–6 were characterised by multinuclear NMR (1H, 13C, 31P) and IR spectroscopy. The former technique revealed the presence of two inequivalent phosphorus atoms in 6r. The molecular structure of 1r confirmed the absolute configuration of the chiral centers and a chair-chair conformation of the heterocycle with equatorial orientation of the substituents on phosphorus and axial on nitrogen atoms. Compound 1s was used to form a palladium catalyst for the co-polymerisation of carbon monoxide and norbornadiene. The structures of the co-polymers obtained were characterised by GPC, 1H and 13C NMR spectroscopy and elemental analysis.

An Effective Methodology of P,N-Macrocycles Design

The Mannich-type condensation in the systems: phosphine-formaldehyde-amine is an effective method of P,N-macrocycles design if bifunctional reagents are used.

Stereoselective Synthesis and Interconversions of 1,9-Diaza-3,7,11,15-Tetraphosphacyclohexadecanes

We report here the novel stereoselective method of design of macrocyclic tetraphosphines, based on the principles of covalent self-assembly.

Stereoselective Synthesis of Novel 18- and 20-Membered P,N-Containing Macrocyclic Phosphine Ligands

Abstract We report here the stereoselective synthesis of novel macrocyclic tetraphosphines, based on the principles of covalent self-assembly.

CCDC 275043: Experimental Crystal Structure Determination

Related Article: A.A.Karasik, R.N.Naumov, A.S.Balueva, Yu.S.Spiridonova, O.N.Golodkov, H.V.Novikova, G.P.Belov, S.A.Katsyuba, E.E.Vandyukova, P.Lonnecke, E.Hey-Hawkins, O.G.Sinyashin|2006|Heteroat.Chem.|17|499|doi:10.1002/hc.20272