Complex Formation during SID and Its Effect on Proton Mobility

Surface-induced dissociation (SID) of protonated peptides is a vibrant, active field of study. Significant focus has been placed on understanding the mechanism of dissociation, with most approaches using equilibrium thermodynamic arguments. Here, we explore the dynamics of SID using atomistic simulations. We find that it is common for complexes of peptide fragments to form following dissociation. An important consequence of complexation is that excess protons are not isolated following initial fragmentation and can participate in subsequent chemical reactions. Our work reveals an alternate mechanism for proton mobility that, to our knowledge, has not been previously observed in simulations

Conformational Control of Initiation Rate in Hoveyda–Grubbs Precatalysts

When the coordinating isopropyl ether of the Hoveyda precatalyst is replaced by a cyclohexyl ether, it is possible to control the substituent’s conformation in either the equatorial or axial position. A stereodivergent synthesis of axial and equatorial cyclohexyl vinyl ethers provided access to new ruthenium metathesis precatalysts by carbene exchange. The conformational disposition of the coordinating aryl ether was found to have a significant effect on the reactivity of the precatalyst in alkene metathesis. The synthesis of four new Ru carbene complexes is reported, featuring either the 1,3-bis­(2,4,6-trimethylphenyl)­dihydroimidazolylidene (H₂IMes) or the 1,3-bis­(2,6-diisopropylphenyl)­dihydroimidazolylidene (SIPr) N-heterocyclic carbene ligand. The conformational isomers in the SIPr series were structurally characterized. Performance testing of all new precatalysts in three different ring-closing metatheses and an alkene cross metathesis illustrated superior performance by the precatalysts bearing axial coordinating ethers. Initiation rates with butyl vinyl ether were also measured, providing a useful comparison to existing Hoveyda-type metathesis precatalysts. Use of conformational control of the coordinating ether substituent provides a new way to modulate reactivity in this important class of alkene metathesis precatalysts