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

ABSTRACT: 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 Mo^VI 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.

SUBMITTER: Zwettler N

PROVIDER: S-EPMC6001527 | biostudies-literature | 2018 May

REPOSITORIES: biostudies-literature

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

Zwettler Niklas N Walg Simon P SP Belaj Ferdinand F Mösch-Zanetti Nadia C NC

Chemistry (Weinheim an der Bergstrasse, Germany) 20180427 28

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 ...[more]

PMID: 29521459

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Project description:Heme hydroperoxidases catalyze the oxidation of substrates by H2O2. The catalytic cycle involves the formation of a highly oxidizing species known as Compound I, resulting from the two-electron oxidation of the ferric heme in the active site of the resting enzyme. This high-valent intermediate is formed upon facile heterolysis of the O-O bond in the initial FeIII-OOH complex. Heterolysis is assisted by the histidine and arginine residues present in the heme distal cavity. This chemistry has not been successfully modeled in synthetic systems up to now. In this work, we have used a series of iron(iii) porphyrin complexes (FeIIIL2(Br), FeIIIL3(Br) and FeIIIMPh(Br)) with covalently attached pendent basic groups (pyridine and primary amine) mimicking the histidine and arginine residues in the distal-pocket of natural heme enzymes. The presence of pendent basic groups, capable of 2nd sphere hydrogen bonding interactions, leads to almost 1000-fold enhancement in the rate of Compound I formation from peracids relative to analogous complexes without these residues. The short-lived Compound I intermediate formed at cryogenic temperatures could be detected using UV-vis electronic absorption spectroscopy and also trapped to be unequivocally identified by 9 GHz EPR spectroscopy at 4 K. The broad (2000 G) and axial EPR spectrum of an exchange-coupled oxoferryl-porphyrin radical species, [FeIV[double bond, length as m-dash]O Por˙+] with g eff ⊥ = 3.80 and g eff ‖ = 1.99, was observed upon a reaction of the FeIIIL3(Br) porphyrin complex with m-CPBA. The characterization of the reactivity of the FeIII porphyrin complexes with a substrate in the presence of an oxidant like m-CPBA by UV-vis electronic absorption spectroscopy showed that they are capable of oxidizing two equivalents of inorganic and organic substrate(s) like ferrocene, 2,4,6-tritertiary butyl phenol and o-phenylenediamine. These oxidations are catalytic with a turnover number (TON) as high as 350. Density Functional Theory (DFT) calculations show that the mechanism of O-O bond activation by 2nd sphere hydrogen bonding interaction from these pendent basic groups, which are protonated by a peracid, involves polarization of the O-O σ-bond, leading to lowering of the O-O σ*-orbital allowing enhanced back bonding from the iron center. These results demonstrate how inclusion of 2nd sphere hydrogen bonding interaction can play a critical role in O-O bond heterolysis.

Dataset Information

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

Publications

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

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