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M-O Bonding Beyond the Oxo Wall: Spectroscopy and Reactivity of Cobalt(III)-Oxyl and Cobalt(III)-Oxo Complexes.

ABSTRACT: Terminal oxo complexes of late transition metals are frequently proposed reactive intermediates. However, they are scarcely known beyond Group?8. Using mass spectrometry, we prepared and characterized two such complexes: [(N4Py)CoIII (O)]+ (1) and [(N4Py)CoIV (O)]2+ (2). Infrared photodissociation spectroscopy revealed that the Co-O bond in 1 is rather strong, in accordance with its lack of chemical reactivity. On the contrary, 2 has a very weak Co-O bond characterized by a stretching frequency of ?659?cm-1 . Accordingly, 2 can abstract hydrogen atoms from non-activated secondary alkanes. Previously, this reactivity has only been observed in the gas phase for small, coordinatively unsaturated metal complexes. Multireference ab-initio calculations suggest that 2, formally a cobalt(IV)-oxo complex, is best described as cobalt(III)-oxyl. Our results provide important data on changes to metal-oxo bonding behind the oxo wall and show that cobalt-oxo complexes are promising targets for developing highly active C-H oxidation catalysts.

SUBMITTER: Andris E

PROVIDER: S-EPMC6618258 | biostudies-literature | 2019 Jul

REPOSITORIES: biostudies-literature

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M-O Bonding Beyond the Oxo Wall: Spectroscopy and Reactivity of Cobalt(III)-Oxyl and Cobalt(III)-Oxo Complexes.

Andris Erik E Navrátil Rafael R Jašík Juraj J Srnec Martin M Rodríguez Mònica M Costas Miquel M Roithová Jana J

Angewandte Chemie (International ed. in English) 20190611 28

Terminal oxo complexes of late transition metals are frequently proposed reactive intermediates. However, they are scarcely known beyond Group 8. Using mass spectrometry, we prepared and characterized two such complexes: [(N4Py)CoIII (O)]+ (1) and [(N4Py)CoIV (O)]2+ (2). Infrared photodissociation spectroscopy revealed that the Co-O bond in 1 is rather strong, in accordance with its lack of chemical reactivity. On the contrary, 2 has a very weak Co-O b ...[more]

PMID: 31083766

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Project description: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.

Dataset Information

M-O Bonding Beyond the Oxo Wall: Spectroscopy and Reactivity of Cobalt(III)-Oxyl and Cobalt(III)-Oxo Complexes.

Publications

M-O Bonding Beyond the Oxo Wall: Spectroscopy and Reactivity of Cobalt(III)-Oxyl and Cobalt(III)-Oxo Complexes.

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