https://scholars.lib.ntu.edu.tw/handle/123456789/606940
Title: | An Anthyridine-Based Pentanitrogen Donor Switches from Mono- To Tetradentate with Pd(II) Ions | Authors: | Su B.-K Liu Y.-H Peng S.-M SHIUH-TZUNG LIU |
Keywords: | Catalyst activity;Ligands;Metal halides;Silver halides;Aryl halides;Arylboronic acids;Dinuclear complex;Insertion products;Metal centres;Monodentate ligands;Palladium ion;Silver salts;Suzuki-Miyaura coupling;Tetradentate;Palladium compounds | Issue Date: | 2021 | Journal Volume: | 40 | Journal Issue: | 24 | Start page/Pages: | 4110-4119 | Source: | Organometallics | Abstract: | Treatment of 5-phenyl-2,8-bis(2-pyridinyl)anthyridine (L) with (PPh3)2PdCl2 or (dppe)PdCl2 in the presence of a silver salt resulted in the formation of [trans-(PPh3)2PdLCl](BF4) (1a), [trans-(PPh3)2PdL(MeCN)](BF4)2 (1b), [trans-(PPh3)2PdLCl](PF6) (1c),or [cis-(dppe)PdLCl](BF4) (4), respectively. The ligand L in these complexes acts as a monodentate ligand with N(10) of anthyridine binding to the metal center. In the presence of PPh3, dinuclear complexes [Pd2L(CH3CN)2Cl2](BF4)2 (2) and [Pd2L(CH3CN)4](BF4)4 (3) readily underwent dechelation to yield 1a,b, respectively, whereas the reaction of 2 with dppe gave 4. On the other hand, treatment of 1a and 4 with S8 in the presence of a sufficient amount of palladium ions provided the corresponding dinuclear complex 2. Furthermore, this kind of substitution is also applicable with the Pd-Me complex [Pd2L(CH3CN)2Me2](BF4)2 (5), which could be prepared from complexation of L with 2 equiv of [(COD)Pd(CH3CN)Me](BF4). Thus, [trans-(PPh3)2PdLMe](BF4) (7) was obtained by the reaction of 5 with PPh3. However, the reaction of PPh3 with [Pd2L(CH3CN)2(MeCO)2](BF4)2 (6), a CO insertion product of 5, gave a messy result. The catalytic activity of these complexes in the Suzuki-Miyaura coupling of aryl halide with arylboronic acid under a CO atmosphere was investigated. Crystal structures of 1c, 4, 5, and 7 are reported to confirm their structural details. This work demonstrates the novelty of L as a hypodentate ligand toward palladium ions. ? 2021 American Chemical Society. |
URI: | https://www.scopus.com/inward/record.uri?eid=2-s2.0-85121037256&doi=10.1021%2facs.organomet.1c00569&partnerID=40&md5=6aa914b127f8307ef2d05bfd07e5c7ff https://scholars.lib.ntu.edu.tw/handle/123456789/606940 |
ISSN: | 02767333 | DOI: | 10.1021/acs.organomet.1c00569 |
Appears in Collections: | 化學系 |
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