Bis(ortho)-chelated bis(phosphanyl)aryl ruthenium(II) complexes containingan eta(1)-P-Monodentate or mu-bridging eta 1-P,eta(1)-P' bonded R-PCHP arene ligand, 1-R-3,5-(CH2PPh2)(2)C6H3 [R = H, Br, or, Si(n-CH2CH2C8F17)(3)] -Cyclometalation reaction intermediates and potential catalysts for use in fluorinated biphasic systems

Mono- and binuclear ruthenium(II) complexes containing ligands derived from the meta-bis(phosphanyl) arene ligand 1R-3,5-(CH2PPh2)(2)C6H3 [R-PCHP: R = H (5), Br (3), or Si(n-CH2CH2C8F17)(3) (4)] have been synthesized and full y characterized. On reaction of equimolar amounts of the ruthenium starting material (e.g. [RuCl2(PPh3)(3)]) and the meta-bis(phosphanyl)arene, comple xes of the type [RuCl{C6H2(CH2PPh2)(2)-2,6-R-4}(PPh3)] are invariably isola ted, which contain only one [C6H3(CH2PPh2)(2)-2,6](-) monoanionic Ligand et a (3)-P,C,P'-bonded to Ru. Monitoring of this reaction by H-1 and P-31 NMR has shown it to proceed via intermediate species having an apparently eta ( 3)-P,C,P'-bonded PCP ligand and a second meter bis(phosphanyl) arene ligand that is either eta (1)-P-bonded or mu-eta (1)-P,eta (1)-P'-bridging betwee n two [RuCl(PCP)] units. The synthesis of the first PCP "pincer"-type ligan d with a polyfluorinated "pony tail" is detailed, viz. compound 4 as well a s the corresponding ruthenium complex [RuCl{(n-C8F17-CH2CH2)(3)Si-PCP}], 7 7. The latter compound is soluble in fluorinated solvents and hence represe nts the first ruthenium "pincer"complex that may find use in fluorinated bi phasic systems.