Reductive Activation of
<i>tripod</i>
Metal Compounds: Identification of Intermediates and Preparative Application
作者:Jürgen Mautz、Katja Heinze、Hubert Wadepohl、Gottfried Huttner
DOI:10.1002/ejic.200700873
日期:2008.3
tripod = CH3C(CH2PPh2)3} when treated with KC8 in THF solution under an argon atmosphere produces a reactive species [“tripodCo0”] (A) which undergoes oxidative additions with stannanes, [tripodCo(H)2(SnBu3)] (4), formed, for example, by addition of Bu3SnH. Silanes, R3SiH, undergo the same type of reaction producing [tripodCo(H)2(SiR3)] (R = Et: 5a; R = Ph: 5b). The solid-state structures of all the
[tripodCoCl2] tripod = CH3C(CH2PPh2)3} 当在 THF 溶液中在氩气氛下用 KC8 处理时会产生反应性物质 [“tripodCo0”] (A),它与锡烷发生氧化加成,[tripodCo(H)2(SnBu3) )] (4),例如,通过添加 Bu3SnH 形成。硅烷,R3SiH,经历相同类型的反应,产生 [tripodCo(H)2(SiR3)](R = Et:5a;R = Ph:5b)。所有化合物 [tripodCo(H)2(ER3)](E = Si,R = Ph;E = Sn,R = Ph,Bu)的固态结构都非常相似。虽然它们含有六配位钴,钴的正式氧化态为 +III,但配位几何不是八面体:异质元素 E 偏离它在八面体配位中的位置约 40°,而其他五个配体,三个磷和两个氢气,分别具有大约 90° 和 180° 的预期配位角。异质元素 E 的偏差使得它接近金属键合的氢原子,导致