| Abstract
| - The novel complexes 10, 11 and 15, 16 arise from reaction of [RuCl2(η6-p-cymene)]2 and [Ru(OAc)2(η6-p-cymene)], respectively, with isopropyl- and cyclohexyl-substituted Binap ligands.
- Reactions of the bis-isopropyl and bis-cyclohexyl alkyl Binap ligands, 8 and 9, respectively,with [RuCl2(η6-p-cymene)]2 afford new dinuclear chloro-bridged Ru compounds which containthe Binap ligands as six- rather than four-electron donors. A backbone double bond proximateto one of the P-donors complexes the metal atom. NMR details of the olefin bonding plusisomerization reactions involving loss of the olefin complexation are reported. Reactions of8 or 9 with [Ru(OAc)2(η6-p-cymene)] result in slow P−C bond cleavage and cyclometalation,instead of affording the anticipated [Ru(OAc)2(Binap)] complex. The new cyclometalatedcomplexes, 15 and 16, contain the complexed R2P−O(CO)CH3 ligand and arise (presumably)via acetate attack at phosphorus with the electrons in the P−C bond moving to the rutheniumatom. The solid-state structure of one of these, the cyclohexyl analogue, 16, is reported andrepresents a rare structural example of a molecule with three different chelate ligands. Thecomplexed R2P−O(CO)CH3 ligand is readily hydrolyzed in wet triflic acid to afford theR2P(OH) donor and an η6-arene ligand (via Ru−C protonation).
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