Ruthenium(III) complexes containing bi- and tridentate phosphorus−nitrogen ligands

• Published in: Canadian journal of chemistry Vol. 92; no. 8; pp. 716 - 723
• Main Authors: Mudalige, Dona C, Ma, Erin S.F, Rettig, Steven J, Patrick, Brian O, James, Brian R
• Format: Journal Article
• Language: English
• Published: Ottawa NRC Research Press 01.08.2014; Canadian Science Publishing NRC Research Press
• Subjects: Chemical elements; Chemical properties; Chemical reactions; Chemical synthesis; Chloroform; complexe N,N′-diméthylacétamide; complexes du Ru(III); Coordination compounds; cristallographie; Crystal structure; Crystallography; Crystals; HCl as oxidant; HCl comme oxydant; Ligands; ligands phosphore−azote; N,N′-dimethylacetamide complex; Nitrogen; Phosphines; phosphorus−nitrogen ligands; Precursors; Protons; Ru(III) complexes; Ruthenium; Ruthenium trichloride; Structure; Canada
• ISSN: 0008-4042; 1480-3291
• DOI: 10.1139/cjc-2013-0539

Air-stable Ru III complexes containing a bidentate aminophosphine ligand (PN) of the type mer-RuCl 3 (PN)(PR 3 ) are made from the precursors RuCl 3 (PR 3 ) 2 (DMA)·DMA (PN = o-diphenylphosphino-N,N′-dimethylaniline (P−N) and (R)-N,N′-dimethyl-1-[o-diphenylphosphinophenyl]ethylamine ((R)-AMPHOS); R = Ph, p-tolyl; DMA = N,N′-dimethylacetamide). With the tridentate bis[o-(N,N′-dimethylamino)phenyl]phenylphosphine (BNP), the product is mer-RuCl 3 (BNP) ( 3 ), while tris[o-(N,N′-dimethylaminophenyl)phosphine (TNP) is unreactive toward the precursor. Crystal structures of mer-RuCl 3 (PN)(PPh 3 ), where PN is P−N ( 2a ), (R)-AMPHOS ( 4a ), and 3 ·CHCl 3 are reported as well as those of (R)-AMPHOS, BNP, and TNP. The Ru III −aminophosphine complexes are the first monomeric Ru III species to be formed via the useful, easily synthesized, air-stable Ru III precursors RuCl 3 (PR 3 ) 2 (DMA)·DMA ( 1a and 1b ); complex 2a is formed also via reaction of HCl with trans-RuCl 2 (P−N)(PPh 3 ). A crystal structure of mer,cis-RuCl 3 (DMA) 2 (PPh 3 )·DMA ( 1c ), a side-product from the synthesis of the Ru III precursor, is also presented and is the first-reported complex of DMA with Ru III . Preliminary data show that the Ru III −aminophosphine complexes in DMA (a proton-accepting solvent) are reduced by H 2 to Ru II species that can react further to form an η 2 -H 2 adduct and then a Ru II -hydridochloro species.