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Title: Divergent reactivity of phosphapalladacycles toward E-H (E = N, P, As) bonds
Authors: Tay, Wee Shan
Li, Yongxin
Pullarkat, Sumod A.
Leung, Pak-Hing
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.
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.
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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