Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400 076.
Dalton Trans. 2010 Aug 21;39(31):7353-63. doi: 10.1039/c003174g. Epub 2010 Jul 6.
Highly efficient palladium precatalysts {[RN{-(CH(2))(n)-pz(3,5-Me)(2)}(2)]PdCl(2)}(m) [m = n = 1; R = 2,6-Me(2)C(6)H(3) (1), 2,4,6-Me(3)C(6)H(2) (2), CH(2)Ph (3) and m = n = 2; R = CH(2)Ph (4)] of a series of homoscorpionate bispyrazolyl ligands for the Suzuki-Miyaura cross-coupling of the more challenging aryl chloride substrates are reported. In particular, the palladium 1-4 precatalysts carried out the Suzuki-Miyaura cross-coupling of a wide variety of aryl chloride substrates bearing electron withdrawing, electron donating and heteroaryl substituents. Remarkably enough, the molecular structure determination of the 1-4 precatalysts by X-ray diffraction studies revealed the presence of anagostic [C-H...Pd] type interactions in the mononuclear 1-3 complexes of methylene bridged bispyrazolyl ligands whereas the ethylene bridged analog 4 yielded an interesting dimeric 20-membered macrometallacyclic complex devoid of any such interaction.
报道了一系列同双（吡唑基）配体的高活性钯前催化剂{[RN{-(CH(2))(n)-pz(3,5-Me)(2)}(2)]PdCl(2)}(m) [m = n = 1; R = 2,6-Me(2)C(6)H(3) (1), 2,4,6-Me(3)C(6)H(2) (2), CH(2)Ph (3) 和 m = n = 2; R = CH(2)Ph (4)]，可用于更具挑战性的芳基氯底物的铃木-宫浦交叉偶联反应。特别是钯 1-4 前催化剂可用于各种带有吸电子、给电子和杂芳基取代基的芳基氯底物的铃木-宫浦交叉偶联反应。值得注意的是，通过 X 射线衍射研究对 1-4 前催化剂的分子结构进行了测定，结果表明在亚甲基桥联双吡唑基配体的单核 1-3 配合物中存在着螯合 [C-H…Pd] 型相互作用，而乙烯桥联类似物 4 则生成了一种有趣的不含任何此类相互作用的 20 元大环金属螯合物。
