Amphiphilicity in Oxygen Atom Transfer Reactions of Oxobis(iminoxolene)osmium Complexes.

Oxobis(iminoxolene)osmium(VI) compounds (Rap)2OsO (Rap = 2-(4-RC6H4N)-4,6-tBu2C6H2O) are readily deoxygenated by phosphines and phosphites to give five-coordinate (Rap)2Os(PR'3) or six-coordinate (Rap)2Os(PR'3)2. Structural data indicate that this net two-electron reduction is accompanied by apparent oxidation of the iminoxolene ligands due to their greater ability to engage in π donation to the reduced deoxy form of the osmium complex. In (Rap)2Os(PR'3)2, the HOMO is a ligand-based combination of the iminoxolene redox-active orbitals, while the LUMO is a highly covalent metal-iminoxolene π* orbital. In the trans isomer, the HOMO is required to be ligand-localized by symmetry, while in the cis isomer, the ligands adopt a conformation that minimizes metal-ligand π* interactions in the HOMO. Kinetic studies indicate that the deoxygenations involve the rate-determining attack of the phosphorus(III) reagent on the five-coordinate oxo complexes. Varying the substituents of the aryl groups on the iminoxolene ligands or on the triarylphosphines has little effect on the rate of oxygen atom transfer, with the best correlation shown between oxygen atom transfer rates and the HOMO-LUMO gap of the oxo complexes. This suggests that the osmium oxo group shows a balance between electrophilic and nucleophilic character in its oxygen atom transfer reactions with phosphorus(III) reagents.

High-valent osmium iminoxolene complexes.

2-(Arylamino)-4,6-di-tert-butylphenols containing 4-substituted phenyl groups (RapH2) react with oxobis(ethylene glycolato)osmium(vi) in acetone to give square pyramidal bis(amidophenoxide)oxoosmium(vi) complexes. A mono-amidophenoxide complex is observed as an intermediate in these reactions. Reactions in dichloromethane yield the diolate (Hap)2Os(OCH2CH2O). Both the glycolate and oxo complex are converted to the corresponding cis-dichloride complex on treatment with chlorotrimethylsilane. The novel bis(aminophenol) ligand EganH4, containing an ethylene glycol dianthranilate bridge, forms the chelated bis(amidophenoxide) complex (Egan)OsO, where the two nitrogen atoms of the tetradentate ligand bind in the trans positions of the square pyramid. Structural and spectroscopic features of the complexes are described well by an osmium(vi)-amidophenoxide formulation, with the amount of π donation from ligand to metal increasing markedly as the co-ligands change from oxo to diolate to dichloride. In the oxo-bis(amidophenoxides), the symmetry of the ligand π orbitals results in only one effective π donor interaction, splitting the energy of the two osmium-oxo π* orbitals and rendering the osmium-oxo bonding appreciably anisotropic.

Highly covalent metal-ligand π bonding in chelated bis- and tris(iminoxolene) complexes of osmium and ruthenium.

The bis(aminophenol) 2,2'-biphenylbis(3,5-di-tert-butyl-2-hydroxyphenylamine) (ClipH4) forms trans-(Clip)Os(py)2 upon aerobic reaction of the ligand with {(p-cymene)OsCl2}2 in the presence of pyridine and triethylamine. A more oxidized species, cis-ß-(Clip)Os(OCH2CH2O), is formed from reaction of the ligand with the osmium(vi) complex OsO(OCH2CH2O)2, and reacts with Me3SiCl to give the chloro complex cis-ß-(Clip)OsCl2. Octahedral osmium and ruthenium tris-iminoxolene complexes are formed from the chelating ligand tris(2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)amino-4-methylphenyl)amine (MeClampH6) on aerobic reaction with divalent metal precursors. The complexes' structural and electronic features are well described using a simple bonding model that emphasizes the covalency of the π bonding between the metal and iminoxolene ligands rather than attempting to dissect the parts into discrete oxidation states. Emphasizing the continuity of bonding between disparate complexes, the structural data from a variety of Os and Ru complexes show good correlations to π bond order, and the response of the intraligand bond distances to the bond order can be analyzed to illuminate the polarity of the bonding between metal and the redox-active orbital on the iminoxolenes. The osmium compounds'π bonding orbitals are about 40% metal-centered and 60% ligand-centered, with the ruthenium compounds' orbitals about 65% metal-centered and 35% ligand-centered.