Work

Ligand and Metal Effects in the Gas‐Phase Fragmentation of Thiomethoxymethyl Complexes

Year: 2024

Type: article

Abstract: While the collision‐induced dissociation (CID) of the mass‐selected cation [(Ph3P)2Pt(CH2SCH3)]+ causes the selective liberation of PPh3, the diphosphine complex [(dppe)Pt(CH2SCH3)]+ (dppe=1,2‐bis(diphenylphosphino)ethane) ejects C2H4, CH2S, and (CH3)2S upon CID. The analogous palladium complexes [(Ph3P)2Pd(CH2SCH3)]+ and [(dppe)Pd(CH2SCH3)]+ show similar reactivity, except that C−H‐bond activation is completely lacking. For other bidentate diphosphine ligands such as dppm, dppv, dppp, dppb, dppbz, dppf, and xantphos, a correlation of the dominant reaction channels with the bite angle is observed. For bite angles > 90°, hydrogen‐atom transfer is favored, as evidenced by an increase in dimethyl‐sulfide loss. For smaller bite angles (< 90°), intramolecular activation of the thiomethoxymethyl ligand predominates, thus resulting in increased losses of thioformaldehyde and ethene. The results of the CID experiments are compared with those for [(bipy)Pt(CH2SCH3)]+, for which the loss of C2H4 is observed as the main process. DFT calculations for the complexes [(dppe)Pt(CH2SCH3)]+ and [(bipy)Pt(CH2SCH3)]+ together with the experimental findings uncover subtle differences in the underlying reaction mechanisms.

Source: European Journal of Inorganic Chemistry

DOI: 10.1002/ejic.202400472

Authors: Gilles Stebens, David Kury, Lukas Jakob, Burkhard Butschke

Institution: University of Freiburg

Language: English

Topic: Mass Spectrometry Techniques and Applications

Subfield: Spectroscopy

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $3,860

Funder: Deutsche Forschungsgemeinschaft