0000000000534947
AUTHOR
Willi Schwotzer
C—br insertion reactions in rhodium and iridium compounds containing an ortho-halo-arylphosphine. X-ray structures of two ortho-metallated compounds of formula IrX2[P(C6F4)Ph2][P(o-BrC6F4)Ph2], (X = Cl, Br)
Abstract A comparative study of the reaction of rh and ir complexes with the ortho-bromo-arylphosphine PCBr [PCBr = P(o-BrC6F4)(C6H5)2], is presented. Various PCBr complexes of Ir(I) and Rh(I) undergo rapid insertion of the metal atom into a CBr bond provided the phosphine is coordinated in a η2-mode (Pbr). If the Br coordination is substituted by a superior ligand such as CO or an olefin, no reaction occurs under normal conditions. PCBr complexes of the tervalent metals require a two-electron reduction step prior to the ortho-metallation reaction. Most intermediates were characterized by chemical and spectroscopic analysis. Two intermediates of general formula IrX2(η2-PC)(η-PCBr), [PC = …
Synthesis of ruthenium(II) compounds with ortho-oxypyridinate ligands (hp). Crystal structure characterization of [Ru(η6-p-CH3C6H4CH(CH3)2)Cl(hp)]
Abstract The reaction of [Ru(η6-p-cymene)Cl2]2 (p-cymene = p-CH3C6H4CH(CH3)2) with Nahp in THF yields [Ru(η6]-p-cymene)Cl(hp)] (1). The crystal structure of (1) has been determined by X-ray methods. (1) crystallizes in the space group Pbca, with a = 16.629(2), b = 10.201(3), c = 17.752(2) A. The compound contains one coordinated arene group, one chlorine and one hp group in a chelating coordination mode. The reaction of (1) with Aghp yields [Ru(η6-p-cymene)(hp)2] (2). The 13C NMR spectrum at - 70°C is consistent with a structure Ru(η6-p-cymene)(η2-hp)(η1-hp). At room temperature a rapid interconvertion between the two hp ligands occurs according to the observed 1H and 13C NMR spectra.