Journal
APPLIED ORGANOMETALLIC CHEMISTRY
Volume 34, Issue 10, Pages -Publisher
WILEY
DOI: 10.1002/aoc.5885
Keywords
Mesoionic; N-heterocyclic thione; non-symmetrical; pincer
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Funding
- High-level Teachers in Beijing Municipal Universities in the Period of 13th Five-year Plan [CITTCD201904087]
- General Project of Scientific Research Program of Beijing Education Commission [KM201810028007]
- Natural Science Foundation of Beijing Municipality [2192012]
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In contrast to well-established symmetrical pincer complexes, non-symmetrical metal pincers with the loss of C(2v)symmetry are much less studied. In this work, mesoionic NHTs (NHTs = N-heterocyclic thiones), which can be viewed as the sulfur adducts of mesoionic carbenes, are incorporated into pincer complexes for the first time. Two symmetrical and non-symmetrical phenylene-bridged bis (NHT) compounds3a/3bwere synthesized as proligands via a cycloaddition-alkylation-thionation reaction sequence. In a case to access bis (NHT) compound3c, N-dealkylation reactions occurred. The carbene NMR signals of NHTs are only partially correlated to the pi-accepting abilities of carbenes, which is different from Bertrand's carbene-phosphinidene system. The structural analysis of3a/3bindicates that they possess C-S partial double bonds.3aand3bserved as the precursors to access two aryl anion-linked [SCS/S '] pincer complexes6a/6b. An external base proved to be essential for this cyclopalladation process. The catalytic properties of6a/6bin the cycloisomerizations of alkynoic acids have been examined. Finally, non-symmetrical complex6ashows superior catalytic performance in such transformations contrasting to its symmetrical counterpart6b.
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