Organometallic C–H Oxidation with O2 Mediated by Soluble Group 10 Metal Complexes

Vedernikov, Andrei N.

doi:10.1007/978-981-32-9751-7_9

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“…The main components of these energy sources are alkanes, which are also the raw materials of the chemical industry. There has been and continues to be much interest to functionalize alkanes through selective C–H bond activation to obtain more valuable organic chemicals under mild conditions. − There are many reports on C–H bond activation using transition-metal complexes. − In this area, homogeneous catalytic systems bearing late transition metals such as palladium − and platinum − are particularly important. The study of direct C–H bond activation is often difficult, and as a result, C–H alkane activation is often investigated through the protonolysis of M–C bonds (i.e., the microscopic reverse of the activation step) in organometallic compounds such as methylplatinum(II) complexes. − …”

Section: Introductionmentioning

confidence: 99%

Ligand-Controlled C_sp²–H versus C_sp³–H Bond Formation in Cycloplatinated Complexes: A Joint Experimental and Theoretical Mechanistic Investigation

et al. 2021

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The cyclometalated platinum(II) complexes [PtMe(C∧N)(L)] [1 PS : C∧N = 2-phenylpyridinate (ppy), L = SMe2; 1 BS : C∧N = benzo[h]quinolate (bhq), L = SMe2; 1 PP : C∧N = ppy, L = PPh3; and 1 BP : C∧N = bhq, L = PPh3] containing two different cyclometalated ligands and two different ancillary ligands have been investigated in the reaction with CX3CO2H (X = F or H). When L = SMe2, the Pt–Me bond rather than the Pt–C bond of the cycloplatinated complex is cleaved to give the complexes [Pt(C∧N)(CX3CO2)(SMe2)]. When L = PPh3, the selectivity of the reaction is reversed. In the reaction of [PtMe(C∧N)(PPh3)] with CF3CO2H, the Pt–C∧N bond is cleaved rather than the Pt–Me bond. The latter reaction gave [PtMe(κ1N–Hppy)(PPh3)(CF3CO2)] as an equilibrium mixture of two isomers. For L = PPh3, no reaction was observed with CH3CO2H. The reasons for this difference in selectivity for complexes 1 are computationally discussed based on the energy barrier needed for the protonolysis of the Pt–Csp 3 bond versus the Pt–Csp 2 bond. Two pathways including the direct one-step acid attack at the Pt–C bond (SE2) and stepwise oxidative–addition on the Pt(II) center followed by reductive elimination [SE(ox)] are proposed. A detailed density functional theory (DFT) study of these protonations along with experimental UV–vis kinetics suggests that a one-step electrophilic attack (SE2) at the Pt–C bond is the most likely mechanism for complexes 1, and changing the nature of the ancillary ligand can influence the selectivity in the Pt–C bond cleavage. The effect of the nature of the acid and cyclometalated ligand (C∧N) is also discussed.

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Section: Introductionmentioning

confidence: 99%

Ligand-Controlled C_sp²–H versus C_sp³–H Bond Formation in Cycloplatinated Complexes: A Joint Experimental and Theoretical Mechanistic Investigation

et al. 2021

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Organometallic C–H Oxidation with O2 Mediated by Soluble Group 10 Metal Complexes

Cited by 1 publication

References 77 publications

Ligand-Controlled C_sp²–H versus C_sp³–H Bond Formation in Cycloplatinated Complexes: A Joint Experimental and Theoretical Mechanistic Investigation

Ligand-Controlled C_sp²–H versus C_sp³–H Bond Formation in Cycloplatinated Complexes: A Joint Experimental and Theoretical Mechanistic Investigation

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Organometallic C–H Oxidation with O2 Mediated by Soluble Group 10 Metal Complexes

Cited by 1 publication

References 77 publications

Ligand-Controlled Csp2–H versus Csp3–H Bond Formation in Cycloplatinated Complexes: A Joint Experimental and Theoretical Mechanistic Investigation

Ligand-Controlled Csp2–H versus Csp3–H Bond Formation in Cycloplatinated Complexes: A Joint Experimental and Theoretical Mechanistic Investigation

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Ligand-Controlled C_sp²–H versus C_sp³–H Bond Formation in Cycloplatinated Complexes: A Joint Experimental and Theoretical Mechanistic Investigation

Ligand-Controlled C_sp²–H versus C_sp³–H Bond Formation in Cycloplatinated Complexes: A Joint Experimental and Theoretical Mechanistic Investigation