title: Reversible α-Hydrogen and α-Alkyl Elimination in PC(sp(3))P Pincer Complexes of Iridium.
abstract: Despite significant progress in recent years, the cleavage of unstrained C(sp(3))-C(sp(3)) bonds remains challenging. A C-C coupling and cleavage reaction in a PC(sp(3))P iridium pincer complex is mechanistically studied; the reaction proceeds via the formation of a carbene intermediate and can be described as a competition between α-hydrogen and α-alkyl elimination; the latter process was observed experimentally and is an unusual way of C(sp(3))-C(sp(3)) bond scission, which has previously not been studied in detail. Mechanistic details that are based upon kinetic studies, activation parameters, and DFT calculations are also discussed. A full characterization of a C-C agostic intermediate is presented.
authors.affiliation: Centre for Analysis and Synthesis, Department of Chemistry, Lund University, PO Box 124, 22100 Lund (Sweden).
authors.forename: Klara J
authors.initials: KJ
authors.lastname: Jonasson
authors.affiliation: Centre for Analysis and Synthesis, Department of Chemistry, Lund University, PO Box 124, 22100 Lund (Sweden).
authors.forename: Alexey V
authors.initials: AV
authors.lastname: Polukeev
authors.affiliation: Division of Theoretical Chemistry & Biology, School of Biotechnology, KTH Royal Institute of Technology, 10691 Stockholm (Sweden).
authors.forename: Rocío
authors.initials: R
authors.lastname: Marcos
authors.affiliation: Division of Theoretical Chemistry & Biology, School of Biotechnology, KTH Royal Institute of Technology, 10691 Stockholm (Sweden).
authors.forename: Mårten S G
authors.initials: MS
authors.lastname: Ahlquist
authors.affiliation: Centre for Analysis and Synthesis, Department of Chemistry, Lund University, PO Box 124, 22100 Lund (Sweden). ola.wendt@chem.lu.se.
authors.forename: Ola F
authors.initials: OF
authors.lastname: Wendt
mesh_terms: D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006859:Hydrogen / Q000737:chemistry*; D007495:Iridium / Q000737:chemistry*; D008968:Molecular Conformation; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D056831:Coordination Complexes; D007495:Iridium; D006859:Hydrogen
keywords: density functional calculations; elimination; iridium; kinetics; pincer complexes