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Title: Synthesis, structures, spectroscopic and electrochemical studies of Ru(II) complexes containing bis(phosphino)amine ligands. Crystal and molecular structures of trans-[RuCl2{Ph2PN(Me)PPh2-κP,κP}2] and trans-[RuCl2{Ph2PN(iPr)PPh2-κP,κP}2]
Keywords: Bis(Phosphino)Amines
Octahedral Complexes
Crystal Structure
Cyclic Voltammetry
Issue Date: 2003
Publisher: Elsevier
Citation: Polyhedron 22(4), 587-593
Abstract: The synthesis, characterization and X-ray crystal study of the monomeric neutral complexes of general formula trans-[RuCl2{Ph2PN(R)PPh2-κP,κP}2] (R = H 1, Me 2, Et 3, nPr 4, iPr 5, nBu 6, Ph 7) is described. The analogous cis complexes, cis-[RuCl2{Ph2PN(R)PPh2-κP,κP}2] (R = H 8, Me 9), have also been synthesized and are characterized. The trans-[RuCl2{Ph2PN(Me)PPh2-κP,κP}2] complex reacts with Ag2SO4 to give a cis neutral complex, [Ru{(SO4)-κO,κO}{Ph2PN(Me)PPh2-κP,κP}2] (10) in good yield. Cyclic voltammograms of the complexes show two one-electron oxidation waves, one being quasi-reversible (RuIII/RuII) and the other chemically irreversible (RuIV/RuIII) with E1/2(RuIII/RuII)cis > E1/2(RuIII/RuII)trans. The more positive (RuIII/RuII) potential for the cis isomer compared to that of trans isomer is consistent with stabilization of the dπ levels in the cis compared to the trans complex.
ISSN: 0277-5387
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