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|Title:||Divergent reactivity of phosphapalladacycles toward E-H (E = N, P, As) bonds||Authors:||Tay, Wee Shan
Pullarkat, Sumod A.
|Keywords:||Science::Chemistry||Issue Date:||2020||Source:||Tay, W. S., Li, Y., Pullarkat, S. A. & Leung, P. (2020). Divergent reactivity of phosphapalladacycles toward E-H (E = N, P, As) bonds. Organometallics, 39(1), 182-188. https://dx.doi.org/10.1021/acs.organomet.9b00723||Project:||M4080454||Journal:||Organometallics||Abstract:||Secondary arsines were observed to decomplex strongly chelating phosphapalladacycles rapidly under mild conditions. As-H bond migration led to ortho-protonation of the C,P ligand. On the other hand, N-H and P-H bonds in amine and phosphine analogues were acidified under the same conditions and no ligand decomplexation of the metallacycle was observed. Subsequently, secondary arsines bearing the As-H bond were applied in deuteration by directed ortho-metalation (DoM) and decomplexation strategies. In the former, HAsPh2 was a convenient deuterium shuttle which facilitated the ortho-deuteration of DoM-palladacycle intermediates under neutral conditions. High deuterium incorporation (>99%) was achieved without specialized preformed deuterating agents. In the latter, HAsPh2 afforded the preligands of monomeric, dimeric, bidentate, and tridentate complexes of Pd in excellent yields of 95-98% within 30 min at room temperature. Key reaction steps for the intramolecular insertion of As-H into the Pd-C bond were outlined, and the effects of regioisomerism on the ortho-protonation pathway were evaluated.||URI:||https://hdl.handle.net/10356/155198||ISSN:||0276-7333||DOI:||10.1021/acs.organomet.9b00723||Rights:||© 2019 American Chemical Society. All rights reserved.||Fulltext Permission:||none||Fulltext Availability:||No Fulltext|
|Appears in Collections:||SPMS Journal Articles|
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