| Abstract
| - The cationic complex [Ru(OTf)(P(OH)Ph2){Ph2P-(η6-arene)}]OTf, 2 (2a = 6‘-diphenylphosphino-1‘-naphthyl-η6(1-6)-naphthalene, 2b = 6,6‘-dimethoxy-2‘-diphenylphosphino-η6(1-6)-biphenyl),is shown to react with water/tert-butyl alcohol/THF mixtures to afford [Ru(P(O)(OH)2{Ph2P-(η6-arene)}]2(OTf)2, 4. The solid-state structure of a derivative, [Ru{P(O)(OH)(OMe)}{Ph2P-(naphthyl-η6-naphthalene}]2(OTf)2, 6, is reported and found to possess extremely asymmetricη6-arene bonding. Complexes 4 and 6, plus a mononuclear dimethoxy analogue, Ru(P(O)(OMe)2(Ph2P-(naphthyl-η6-naphthalene)](OTf), 8, represent the first examples of Ru-compounds that contain the phosphorus acid anion P(O)(OR)2 (R = H and/or Me) as ananionic P-donor ligand. PGSE diffusion measurements are shown to be helpful in distinguishing between dinuclear oxygen bridging species and their mononuclear analogues.
- The cationic complex 2a reacts with water/tert-butyl alcohol/THF mixtures to afford the dimer 4a, which contains the unusual anionic ligand P(O)(OH)2, due to the cleavage of two P-phenyl groups.
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