Synthesis of Calcium and Ytterbium Complexes Supported by a Tridentate Imino-Amidinate Ligand and Their Application in the Intermolecular Hydrophosphination of Alkenes and Alkynes
Synthesis of Calcium and Ytterbium Complexes Supported by a Tridentate Imino-Amidinate Ligand and Their Application in the Intermolecular Hydrophosphination of Alkenes and Alkynes
复制标题
三齿亚氨基脒配体负载钙镱配合物的合成及其在烯烃和炔烃分子间氢膦化中的应用
DOI：
10.1021/om201223j
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发表时间：
2012-02-13
期刊：
影响因子：
2.8
通讯作者：
Cui, Chunming
中科院分区：
文献类型：
--
作者：
Hu, Hongfan;Cui, Chunming
合成并表征了钙镱配合物[{2-NC（Ph）NArC6H4CHNAr} M {N（SiMe3）2}（THF）]（M = Ca，Yb; Ar = 2，6-iPr2C6H3）。它们在温和条件下以高活性和高选择性催化烯烃、二烯烃和炔烃的分子间氢膦化反应。用这两种催化剂都观察到对所考察的共轭二烯的高选择性1，4-加成（94 - 100%）。钙络合物专门催化反加成到炔，包括末端炔，而镱，在大多数情况下，催化顺加成。钙催化剂在相对温和的条件下可促进二苯乙烯等受阻烯烃的膦氢化反应。
Well-defined calcium and ytterbium complexes [{2-NC(Ph)NArC6H4CHNAr}M{N(SiMe3)2}(THF)] (M = Ca, Yb; Ar = 2,6-iPr2C6H3) have been synthesized and characterized. They catalyze the intermolecular hydrophosphination of alkenes, dienes, and alkynes with high activity and selectivity under mild conditions. Highly selective 1,4-additions (94–100%) for the conjugated dienes examined have been observed with both catalysts. The calcium complex exclusively catalyzes anti addition to alkynes, including terminal alkynes, while the ytterbium, in most cases, catalyzes syn addition. The calcium catalyst could promote hydrophosphination of hindered alkenes such as stilbene under relatively mild conditions.