Semiempirical method for examining asynchronicity in metal-oxido-mediated C-H bond activation.

The oxidation of substrates via the cleavage of thermodynamically strong C-H bonds is an essential part of mammalian metabolism. These reactions are predominantly carried out by enzymes that produce high-valent metal-oxido species, which are directly responsible for cleaving the C-H bonds. While much is known about the identity of these transient intermediates, the mechanistic factors that enable metal-oxido species to accomplish such difficult reactions are still incomplete. For synthetic metal-oxido species, C-H bond cleavage is often mechanistically described as synchronous, proton-coupled electron transfer (PCET). However, data have emerged that suggest that the basicity of the M-oxido unit is the key determinant in achieving enzymatic function, thus requiring alternative mechanisms whereby proton transfer (PT) has a more dominant role than electron transfer (ET). To bridge this knowledge gap, the reactivity of a monomeric MnIV-oxido complex with a series of external substrates was studied, resulting in a spread of over 104 in their second-order rate constants that tracked with the acidity of the C-H bonds. Mechanisms that included either synchronous PCET or rate-limiting PT, followed by ET, did not explain our results, which led to a proposed PCET mechanism with asynchronous transition states that are dominated by PT. To support this premise, we report a semiempirical free energy analysis that can predict the relative contributions of PT and ET for a given set of substrates. These findings underscore why the basicity of M-oxido units needs to be considered in C-H functionalization.

Selective C-H Bond Cleavage with a High-Spin FeIV-Oxido Complex.

Non-heme Fe monooxygenases activate C-H bonds using intermediates with high-spin FeIV-oxido centers. To mimic these sites, a new tripodal ligand [pop]3- was prepared that contains three phosphoryl amido groups that are capable of stabilizing metal centers in high oxidation states. The ligand was used to generate [FeIVpop(O)]-, a new FeIV-oxido complex with an S = 2 spin ground state. Spectroscopic measurements, which included low-temperature absorption and electron paramagnetic resonance spectroscopy, supported the assignment of a high-spin FeIV center. The complex showed reactivity with benzyl alcohol as the external substrate but not with related compounds (e.g., ethyl benzene and benzyl methyl ether), suggesting the possibility that hydrogen bonding interaction(s) between the substrate and [FeIVpop(O)]- was necessary for reactivity. These results exemplify the potential role of the secondary coordination sphere in metal-mediated processes.

Heterolytic Si-H Bond Cleavage at a Molybdenum-Oxido-Based Lewis Pair.

The reaction of a molybdenum(VI) oxido imido complex with the strong Lewis acid B(C6 F5 )3 gave access to the Lewis adduct [Mo{OB(C6 F5 )3 }(NtBu)L2 ] featuring reversible B-O bonding in solution. The resulting frustrated Lewis pair (FLP)-like reactivity is reflected by the compound's ability to heterolytically cleave Si-H bonds, leading to a clean formation of the novel cationic MoVI species 3 a (R=Et) and 3 b (R=Ph) of the general formula [Mo(OSiR3 )(NtBu)L2 ][HB(C6 F5 )3 ]. These compounds possess properties highly unusual for molybdenum d0 species such as an intensive, charge-transfer-based color as well as a reversible redox couple at very low potentials, both dependent on the silane used. Single-crystal X-ray diffraction analyses of 2 and 4 b, a derivative of 3 b featuring the [FB(C6 F5 )3 ]- anion, picture the stepwise elongation of the Mo=O bond, leading to a large increase in the electrophilicity of the metal center. The reaction of 3 a and 3 b with benzaldehyde allowed for the regeneration of compound 2 by hydrosilylation of the benzaldehyde. NMR spectroscopy suggested an unusual mechanism for the transformation, involving a substrate insertion in the B-H bond of the borohydride anion.

A di­iron(III) µ-oxido complex as catalyst precursor in the oxidation of alkanes and alkenes.

The oxido-bridged diiron(III) complex [Fe2(µ-O)(µ-OAc)(DPEAMP)2](OCH3) (1), based on a new unsymmetrical ligand with an N4O donor set, viz. [2-((bis(pyridin-2-ylmethyl)amino)methyl)-6-((ethylamino)methyl)-4-methylphenol (HDPEAMP)], has been prepared and characterized by spectroscopic methods and X-ray crystallography. The crystal structure of the complex reveals that each Fe(III) ion is coordinated by three nitrogen and three oxygen donors, two of which are the bridging oxido and acetate ligands. Employing H2O2 as a terminal oxidant, 1 is capable of oxidizing a number of alkanes and alkenes with high activity. The catalytic oxidation of 1,2-dimethylcyclohexane results in excellent retention of configuration. Monitoring of the reaction of 1 with H2O2 and acetic acid in the absence of substrate, using low-temperature UV-Vis spectroscopy, suggests the in situ formation of a transient Fe(III)2-peroxido species. While the selectivity and nature of oxidation products implicate a high-valent iron-oxido complex as a key intermediate, the low alcohol/ketone ratios suggest a simultaneous radical-based process.