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Bis( ortho )‐Chelated Bis(phosphanyl)aryl Ruthenium(II) Complexes Containing an η 1 ‐ P ‐Monodentate or μ‐Bridging η 1 ‐ P ,η 1 ‐ P′ Bonded R−PCHP Arene Ligand, 1‐R‐3,5‐(CH 2 PPh 2 ) 2 C 6 H 3 [R = H, Br, or, Si( n ‐CH 2 CH 2 C 8 F 17 ) 3 ] — Cyclometalation Reaction Intermediates and Potential Catalysts for Use in Fluorinated Biphasic Systems
Author(s) -
Dani Paulo,
Richter Bodo,
van Klink Gerard P. M.,
van Koten Gerard
Publication year - 2001
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(20011)2001:1<125::aid-ejic125>3.0.co;2-q
Subject(s) - chemistry , ruthenium , pincer movement , ligand (biochemistry) , aryl , bridging ligand , denticity , pincer ligand , chelation , medicinal chemistry , stereochemistry , metal , catalysis , organic chemistry , receptor , biochemistry , alkyl
Mono‐ and binuclear ruthenium( II ) complexes containing ligands derived from the meta ‐bis(phosphanyl)arene ligand 1‐R‐3,5‐(CH 2 PPh 2 ) 2 C 6 H 3 [R−PCHP: R = H ( 5 ), Br ( 3 ), or Si( n ‐CH 2 CH 2 C 8 F 17 ) 3 ( 4 )] have been synthesized and fully characterized. On reaction of equimolar amounts of the ruthenium starting material (e.g. [RuCl 2 (PPh 3 ) 3 ]) and the meta ‐bis(phosphanyl)arene, complexes of the type [RuCl{C 6 H 2 (CH 2 PPh 2 ) 2 ‐2,6‐R‐4}(PPh 3 )] are invariably isolated, which contain only one [C 6 H 3 (CH 2 PPh 2 ) 2 ‐2,6] − monoanionic ligand η 3 ‐ P,C,P′ ‐bonded to Ru. Monitoring of this reaction by 1 H and 31 P NMR has shown it to proceed via intermediate species having an apparently η 3 ‐ P,C,P′ ‐bonded PCP ligand and a second meta ‐bis(phosphanyl)arene ligand that is either η 1 ‐P‐bonded or μ‐η 1 ‐P,η 1 ‐P′‐bridging between two [RuCl(PCP)] units. The synthesis of the first PCP “pincer”‐type ligand with a polyfluorinated “pony tail” is detailed, viz. compound 4 as well as the corresponding ruthenium complex [RuCl{( n ‐C 8 F 17 CH 2 CH 2 ) 3 Si−PCP}], 7 . The latter compound is soluble in fluorinated solvents and hence represents the first ruthenium “pincer” complex that may find use in fluorinated biphasic systems.