Synthesis, Reactivity, X‐ray Crystal Structures and Electrochemical Behaviour of Water‐Soluble [Tris(pyrazolyl)borato]ruthenium(II) Complexes of 1,3,5‐Triaza‐7‐phosphaadamantane (PTA)

Abstract

A series of chloridoruthenium(II) complexes bearing the tripodal ligand tris(pyrazolyl)borate (Tp), the water‐soluble cage phosphane 1,3,5‐triaza‐7‐phosphaadamantane (PTA) and its N‐boranyl adduct PTA(BH3), together with PPh3, have been synthesised. The corresponding monohydrido complexes have also been obtained by treating the chlorides withNaOMe. The X‐ray crystal structures of [TpRuCl(PTA)(PPh3)] (2) and [TpRuCl(PTA)2] (3) are also described. Cyclic voltammetry (CV) studies in MeCN and dmso generally show reversible RuII/III oxidation waves and the values of E1/2ox reflect the electron‐donating character of the ligands [Tp (each arm) > PTA > PTA(BH3)], whose Lever electrochemical parameter (EL) has been estimated for the first time.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Formation of Oxaphosphacarbenes by Reaction of [RuTpCl(PPh3)(thp)] with Terminal Alkynes and a Propargylic Alcohol

“…NMR spectra were taken on a Bruker AMX 400 instrument. Chemical shifts are given in parts per million with reference to SiMe 4 (500 mg, 0.57 mmol) in thf (40 mL). The mixture was stirred and heated at reflux for 1 h. The resultant yellow solution was filtered through Celite to remove the decomposition products.…”

“…may induce intramolecular attack on the unsaturated carbon chain to afford new series of metal complexes in which the carbene moiety is part of a chelate ligand [3] (Scheme 1). Continuing our studies on {TpRu} moieties, [4] we report on the reactions of TpRu complexes [Tp = hydrotris(pyrazolyl)borate], containing the tris(hydroxymethyl)phosphane OH)}(PPh 3 )]Cl [RЈЈ = CH 2 Ph (3b), CH 2 C 6 H 4 Me (4b), CH 3 (5b), respectively]. Compound 7a showed a very high tendency to eliminate formaldehyde.…”

Investigating the reactivity of neutral water-soluble Ru(ii)–PTA carbonyls towards the model imine ligands pyridine and 2,2′-bipyridine

“…not included in polydentate ligands. 5b, [36][37][38][39][40] Only recently the group of Romerosa described a series of neutral Ru(II)-PTA half-sandwich compounds that bear a natural purine bound through the N7 or N9 of the imidazolic ring. 41 When trans,trans,trans-[RuCl 2 (CO)(OH 2 )(PTA) 2 ] (1) was treated with a slight excess of pyridine in water at room temperature, the yellow complex trans,trans,trans-[RuCl 2 (CO)(py)(PTA) 2 ] (7) was selectively obtained upon evaporation of the solvent (Scheme 1) and fully characterized by ESI-MS, NMR, and IR spectroscopies (ESI †).…”

Stereoisomeric Control in [RuCl2(PTA)2(2L)] Complexes (2L=2py or bpy): From Theoretical Calculations to a 2+2 Metallacycle of Pyridylporphyrins

“…Whereas there are very few examples of Ru(II)‐PTA coordination compounds in the literature with monodentate pyridine or azole ligands, [40] i. e. not included in polydentate moieties, [12,44–49] those with chelating diimine ligands are relatively more abundant. Stereoisomeric derivatives such as mer ‐ and fac ‐[Ru(bpy)Cl(PTA) 3 ](PF 6 ), and cis ‐ and trans ‐[Ru(bpy) 2 (PTA) 2 ](PF 6 ) 2 were prepared by us and by Romerosa and co‐workers [36,50–52] .…”