This article discusses synthesis and reactivity of a coordinatively unsaturated Ruthenium(II) parent amido complex. The five-coordinate parent amido complex (PCP)Ru(CO)(NH2) (2) (PCP = 2,6-(CH2P-tBu2)2C6H3) has been prepared by two independent routes that involve deprotonation of Ru(II) ammine complexes. Complex 2 reacts with phenylacetylene to yield the Ru(II) acetylide complex (PCP)Ru(CO)(C≡CPh) (5) and ammonia. In addition, complex 2 rapidly activates dihydrogen at room temperature to yield ammonia and the previously reported hydride complex (PCP)Ru(CO)(H). The ability of the amido complex 2 to cleave the H-H bond is attributed to the combination of a vacant coordination site for binding/activation of dihydrogen and a basic amido ligand. Complex 2 also undergoes an intramolecular C-H activation of a methyl group on the PCP ligand to yield ammonia and a cyclometalated complex. The reaction of (PCP)Ru(CO)(CI) with MeLi allows the isolation of (PCP)Ru(CO)(Me) (8), and complex 8 undergoes an intramolecular C-H activation analogous to the amido complex 2 to produce methane and the cyclometalated complex. Determination of activation parameters for the intramolecular C-H activation transformations of 2 and 8 reveal identical ∆Hǂ {18(1) kcal/mol} with ∆Sǂ = -23(4) eu and -18(4) eu, respectively. Density functional theory has been applied to the study of intermolecular activation of methane and dihydrogen by (PCP')Ru(CO)(NH2) to yield (PCP')Ru(CO)(NH3)(X) (X = Me or H; PCP' = 2,6-(CH2-PH2)2C6H3). The results indicate that the activation of dihydrogen is both exoergic and exothermic. In contrast, the addition of a C-H bond of methane across the Ru-NH2 bond has been calculated to be endoergic and endothermic. The surprising endoergic nature of the methane C-H activation has been attributed to a large and unfavorable change in Ru-N bond dissociation energy upon conversion from Ru-amido to Ru-ammine.

Reprinted with permission from Organometallics. Copyright 2004 American Chemical Society.

10 p.

• English

• DOI: 10.1021/om049836r
• ARK: ark:/67531/metadc77183