The Synthesis and Characterisation of Bis(phosphane)‐Linked (⁶‐p‐Cymene)ruthenium(II)–Borane Compounds

Abstract

The reaction of [(η6‐p‐cymene)RuCl2]2 with some bis(phosphane) ligands (dppm, dppe, dppv, dppa, dpp14b, dppf) has been investigated. In general mixtures of products were obtained, although the pendant phosphane complexes [(η6‐p‐cymene)RuCl2(η1‐dppv)] and [(η6‐p‐cymene)RuCl2(η1‐dppa)] were isolated and characterized in the solid state by X‐ray diffraction. The later complex was obtained in lower yield and undergoes an equilibration reaction resulting in the formation of a dimeric species, where the dppa bridges two ruthenium centres, and uncoordinated phosphane; the bridging species was also structurally characterised in the solid state. In contrast, the reaction of [(η6‐p‐cymene)RuCl2(PPh3)] with dppa in the presence of [NH4]PF6 results in the formation of [(η6‐p‐cymene)RuCl(PPh3)(η1‐dppa)]PF6, which is stable in solution. A series of linked ruthenium–borane complexes, viz. [(η6‐p‐cymene)RuCl2(η1‐phosphane‐BH3)] (phosphane = dppm, dppe, dppv, dppa, dpp14b, dppf) and [(η6‐p‐cymene)RuCl(PPh3)(η1‐dppa‐BH3)]PF6 have been prepared from isolated pendant phosphane complexes, those generated in situ, or from a preformed phosphane–borane adduct. The solid‐state structures of [(η6‐p‐cymene)RuCl2(η1‐dppm‐BH3)], [(η6‐p‐cymene)RuCl2(η1‐dppe‐BH3)] and [(η6‐p‐cymene)RuCl2(η1‐dppv‐BH3)] have been determined by X‐ray diffraction analysis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Half Sandwich Electron Deficient N,N′,N′′‐Triarylguanidinatoruthenium(II) Complexes: Syntheses, Reactivity Studies, and Structural Aspects

“…0.054(8) Å found in 10 are comparable with the corresponding values observed for 3 within the 3σ cut off. The bond parameters pertinent to DPPA in 10 are comparable with those parameters published for the related complex, [(η 6 ‐ p ‐cymene)RuCl 2 (κ 1 P ‐Ph 2 PC≡CPPh 2 )] …”

Cyclopentadienyl Ruthenium(II) Complexes with Bridging Alkynylphosphine Ligands: Synthesis and Electrochemical Studies

“…[9] Remarkably, the only complex containing a diphosphinoalkyne ligand is Dysons compound [{(pcymene)RuCl 2 } x A C H T U N G T R E N N U N G (dppa)] (x = 1,2; dppa = diphenylphosphinoacetylene). [10] With the aim of expanding on this theme and these architectures, we report here results on the synthesis and structural characterisation of a family of cyclopentadienyl ruthenium(II) (CpRu) complexes with the biand tridentate phosphines 1,4-bis[(diphenylphosphino)eth-A C H T U N G T R E N N U N G ynyl]benzene (dppab, 1) and 1,3,5-tris[(diphenylphosphino)-A C H T U N G T R E N N U N G ethynyl]benzene (tppab, 2, and Scheme 1).…”

“…In fact, the par-A C H T U N G T R E N N U N G tially oxidised bi-and trinuclear compounds behave exactly as the parent mononuclear cation [10] + and can thus be classified as Robin-Day class I mixed-valence complexes with a localised charge.…”

“…[10] A solution of a 1:2 ratio between [CpRuA C H T U N G T R E N N U N G (PPh 3 ) 2 Cl] and 1 in toluene heated at reflux did not yield 6, but rather gave the diruthenamacrocycle 7 as a single stable thermodynamic product. Complex 7 is likely to form through intermolecular thermal replacement of the triphenylphosphine ligand in 6 by the pending P donor atom of a second equivalent of the same ruthenium complex.…”

Recent Advances in Dppf‐Containing (Cp/Cp∗)Ru and (Arene)Ru(II) Complexes: Structure, Reactivity, Catalysis, and Electrochemistry (2000–2005)

“…which the dangling phosphorous atom bonded by one BH 3 . [43] For example, reaction of dppf with [( p-cymene)RuCl 2 ] 2 dimer at 08C in CH 2 Cl 2 , followed by addition of BH 3 . THF, then warmed to room temperature for 1 h, gave an unidentate diphosphine coordinated complex [( p-Cymene)Ru(h 1 -PPh 2 C 5 H 4-FeC 5 H 4 PPh 2 BH 3 )Cl 2 ] (35).…”