PtII as a proton shuttle during C–H bond activation in the Shilov process

Abstract

The C-H activation in Shilov's system on cis- and trans-PtCl(2)(H(2)O)(CH(4)) was investigated by ab initio molecular dynamics in water. Simulations revealed an easy C-H bond cleavage forming a transient 5-coordinated species Pt(H)Cl(2)(H(2)O)(CH(3)) that spontaneously releases a proton to the bulk solution.

The Electronics of CH Activation by Energy Decomposition Analysis: From Transition Metals to Main-Group Metals

“…An ab initio molecular dynamics (AIMD) study by Vidossich, Ujaque, and Lled os examined the reaction pathway for methane reacting with Cl 2 Pd(H 2 O) [58]. This study verified that this and similar Pt(II) complexes act as electrophiles towards methane.…”

Recent advances in the application of group-10 transition metal based catalysts in C–H activation and functionalization

“…In the process, the first step (C-H activation) is reported to be the rate determining step of the catalytic cycle [72]. In a recent atomistic simulation study on the Shilov system cis-and trans-PtCl2(H2O)(CH4) σ-complexes within a realistic solvent environment shows that the complexes easily release a proton to the bulk solution [73].…”

Shilov alkane platinum chemistry: 45 years

“…It is worth noting that the Rh I. CH 4 σ-complex is isoelectronic with the Pt II. CH 4 σ-complex assumed to be formed in methane reactions with Pt II compounds [35]. …”

“…Early proofs for the formation of similar complexes involved not only the observation of multiple deuterium exchange and analysis of possible mechanisms but also an occurrence of the reverse isotope effect in the elimination reactions of alkyl hydride complexes [34]. The recent DFT calculations of the Shilov reaction have confirmed an easy cleavage of the C-H bond in the initial σ-complex PtCl 2 (H 2 O)(CH 4 ) (B) to form short-lived five-coordinated Pt IV methylhydride intermediate Pt(H)Cl 2 (H 2 O)(CH 3 ) which in the next stage (C) spontaneously releases H + to the solution bulk[35]. the first methane σ-complex (Scheme 2, M = Rh) was obtained by protonation of the Rh I -CH 3 complex in a CDFCl 2 solution at -110 o C and characterized by NMR since it has a rather long lifetime under these conditions[36].…”