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. 2009 Mar 4;131(8):2762-3.
doi: 10.1021/ja8100825.

C-H bond cleavage with reductants: re-investigating the reactivity of monomeric Mn(III/IV)-oxo complexes and the role of oxo ligand basicity

Trenton H Parsell  1 , Meng-Yin Yang, A S Borovik
Affiliations

C-H bond cleavage with reductants: re-investigating the reactivity of monomeric Mn(III/IV)-oxo complexes and the role of oxo ligand basicity

Trenton H Parsell et al. J Am Chem Soc. .

Abstract

The thermodynamic properties of structurally similar Mn(III) and Mn(IV) complexes have been reinvestigated to understand their reactivity with substrates having C-H bonds. The complexes have the general formula [MnH(3)buea(O)](n-), where [H(3)buea](3-) is the tripodal ligand, tris[(N'-tert-butylureaylato)-N-ethylene]aminato. These complexes are unique because of the intramolecular hydrogen-bonding (H-bond) network surrounding the Mn-oxo units. The redox potentials for the Mn(III/IV)(O) couple was incorrectly assigned in earlier reports: the corrected value is -1.0 V vs Cp(2)Fe(+)/Cp(2)Fe in DMSO, while the Mn(IV/V)(O) process is -0.076 under the same conditions. The oxo ligand in the Mn(III)(O) complexes is basic with a pK(a) of 28.3; the basicity of the terminal oxo ligand in the Mn(IV)(O) complex is estimated to be approximately 15. These values were used to re-evalulate the O-H bond dissociation energy (BDE(OH)) of the corresponding Mn(II/III)-OH complexes: BDE(OH) values of 89 and 77 kcal/mol were determined for [Mn(III)H(3)buea(OH)](-) and [Mn(II)H(3)buea(OH)](2-), respectively. Both Mn(O) complexes react with 9,10-dihydroanthracene (DHA) to produce anthracene in nearly quantitative yields. This is surprising based on the low redox potiental of the complexes, suggesting the basicity of the oxo ligand is a major contributor to the observed reactivity. In contrast to the thermodynamic results, a comparative kinetic investigation found that the Mn(III)(O) complex reacts nearly 20 times faster than the Mn(IV)(O) complex. Activation parameters, determined from an Eyring analysis, found that the entropy of activation is significantly different between the two systems (DeltaDeltaS(++) = -35 eu, where DeltaDeltaS(++) = DeltaS(++)(Mn(IV)(O)) - DeltaS(++)(Mn(III)(O)). This unusual kinetic behavior can be explained in the context of the basicity of the oxo ligands that leads to different mechanisms: for [Mn(III)H(3)buea(O)](2-) a proton transfer-electron transfer mechanism is proposed, whereas for [Mn(IV)H(3)buea(O)](-) a hydrogen-atom transfer pathway is likely.

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Figures

Figure 1
Figure 1
The MnIII/IV(O) and MnII/III (OH) complexes investigated.
Figure 2
Figure 2
Kinetic data for [MnIIIH3buea(O)]2- (black) and [MnIVH3buea(O)]- (blue) at various temperatures (A) and Eyring plot (B). Temperature key (°C): 20(●); 30(■); 40(◆); 50(▲).
Scheme 1
Scheme 1
Reactions of DHA with the MnIII/IV (O) complexes in DMSO.
Scheme 2
Scheme 2
Proposed mechanism for the reaction of [MnIIIH3buea(O)]2- with DHA.
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