Synthesis and reactivity of a coordinatively unsaturated ruthenium(II) parent amido complex: Studies of X-H activation (X = H or C)

被引:93
作者
Conner, D
Jayaprakash, KN
Cundari, TR
Gunnoe, TB [1 ]
机构
[1] N Carolina State Univ, Dept Chem, Raleigh, NC 27695 USA
[2] Univ N Texas, Dept Chem, Denton, TX 76203 USA
关键词
D O I
10.1021/om049836r
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The five-coordinate parent amido complex (PCP)Ru(CO)(NH2) (2) (PCP = 2,6-(CH2P-(BU2)-B-t)(2)C6H3) 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)(Cequivalent toCPh) (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)(Cl) 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 DeltaH(not equal) {18(1) kcal/mol} with DeltaS(not equal) = - 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 = Me or H; PCP' = 2,6-(CH2-PH2)(2)C6H3). 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.
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页码:2724 / 2733
页数:10
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