Divergent reactivity of phosphapalladacycles toward E-H (E = N, P, As) bonds

• المؤلفون الرئيسيون: Tay, Wee Shan, Li, Yongxin, Pullarkat, Sumod A., Leung, Pak-Hing
• مؤلفون آخرون: School of Physical and Mathematical Sciences
• التنسيق: مقال
• اللغة: English
• منشور في: 2022
• الموضوعات: Science::Chemistry; Phosphorus Compounds; Protonation
• الوصول للمادة أونلاين: https://hdl.handle.net/10356/155198
• المؤسسة: Nanyang Technological University

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.