The design of a ruthenium-terpyridine complex having 4-aminobenzyl-diphenylphosphine as remote ligands in a trans arrangement ([Ru(trans-PN)2(trpy)Cl]+Cl−, [trans-bis(aminodiphenylphosphine) terpyridine-Ru(II)Cl]+Cl−) is shown to be a highly versatile approach for the immobilization of the organometallics at a carbon surface. Three distinct strategies could be then successfully employed to achieve the grafting of the complex, namely i) the electroreduction of the corresponding in situ produced diazonium cation, ii) the electrooxidation of the aromatic amine moiety in the presence of a base and iii) an anodic electropolymerization in the absence of base. The modified surfaces were characterized by electrochemical or Scanning Electron Microscopy (SEM) studies. The reported approach allows a clean modulation of film thickness and anchoring modes, particularly useful for a given design of ruthenium containing films dedicated to a given application. In this context, the polymer films which contain the largest surface concentration of active ruthenium were employed as immobilized catalyst for oxidation of benzyl alcohol in water, allowing a test of the catalytic activity of the complexes as grafted materials.

Phosphine–borane moieties with amino-anchoring groups were covalently grafted on glassy carbon substrates, using free radical electrografting methods. The oxidative destruction of phosphine was efficiently quenched thanks to the borane protecting group. The chelating ability of the attached phosphine ligands was exemplified with Mn.

Two novel tetrathiafulvalene (TTF) ligands, substituted by four diphenylphosphinoalkylthio groups, have been synthesized and characterized. Their redox properties, determined by cyclic voltammetry, have been compared with their precursors and discussed. The ability of these redox active ligands to react with two equivalent of cis-W(CO)(4)(C5H11N)(2) is presented. X-ray crystal structure of a bis 13-metallamacrocycle is reported together with its redox behaviour. (C) 2009 Elsevier B.V. All rights reserved.

Redox-active 17- and 19-membered metallamacrocycles were prepared thanks to the chelating ability of bis[(diphenylphosphane)alkylthio]TTF towards the M(CO)(4) fragment (M = Mo, W). The TTF unit can adopt either a cis or a trans configuration as can the phosphorus atoms coordinated to the metal center. Moreover, an element of planar chirality is generated by the trans isomer of the TTF. Thus, the reaction affords six stereoisomers as evidenced by P-31 NMR and Xray crystallographic analyses. The electrochemical properties of the title compounds have been investigated by cyclic voltammetry. Within the 19-membered metallamacrocycles, no significant influence of the two redox moieties was detected, whereas in the 17-membered metallamacrocycles, the oxidized TTF modifies the redox behavior of the metal center. Two crystalline complexes obtained with tetracyanoquinodimethane (TCNQ) and the tungsten 17- and 19-membered metallamacrocycles are reported. Comparison of the crystal structures shows that these metallamacrocycles appear to be rather flexible even with strained structures.

The synthesis of novel (P,S)-ligands containing tetrathiafulvalene (TTF) from preformed TTF derivatives is reported. These compounds were prepared by using borane as protecting group for the phosphine. The electrochemical properties of these new ligands are presented.

Phosphines bearing an aldehyde, a ketone or a carboxyl on the side chain can be prepared by oxidation of the hydroxyalkylphosphine-borane complexes followed by decomplexation using dietkylamine.

Silylated compounds react with AsCl 3 to give dichloroarsines which are dehydrochlorinated and trapped with a diene or a diazocompound.