Introduction of Heteroatoms Based on New Catalyst Activities of Lanthanide Complexes

1. 镧系酰胺配合物催化烯烃氢硅化反应及共轭二烯脱氢双硅化反应。镧系亚胺配合物[Yb(η^2-ph_2CNPh)(hmpa)_3](1)和二胺配合物以1和等摩尔量的Ph_2NH为原料，可有效催化烯烃与PhSiH_3和Ph_2SiH_2的硅氢化反应。另一方面，催化剂诱导共轭二烯的脱氢双硅化反应选择性地得到1,4-双（硅基）-2-丁烯，而不是预期的1,4-和1,2-硅氢化产物。研究发现，催化剂与氢硅烷同时生成氢化物和硅基[Yb[-H]和[Yb]-Si，前者主要与烯烃反应，后者主要与二烯烃反应。镧系-亚胺配合物催化炔的氢化反应及相关碳-碳多键反应。用yb -亚胺配合物1催化炔与二苯基膦的分子间加氢磷化反应，在温和条件下以良好的收率得到烯基膦和氧化膦。该反应也适用于各种碳-碳多键，如共轭二炔和二烯、烯和苯乙烯衍生物。本反应的区域选择性和立体选择性以及范围和限制明显不同于相应的自由基反应。相反，反应是通过将炔插入到Yb-PPh_2上，然后进行质子化反应。事实上，由亚胺配合物和磷化氢得到Yb-磷化物配合物[Yb(PPh_2)_2(hmpa)_3]，该配合物对氢磷化反应具有相似的催化活性。至少在标准条件下，经验速率定律是v=k[催化剂]^2[炔烃]^1[膦]^0。

1. Hydrosilylation of Olefins and Dehydrogenative Double Silylation of Conjugated Dienes Catalyzed by Lanthanide Amide Complexes.Lanthanide-imine complex, [Yb(η^2-ph_2CNPh)(hmpa)_3] (1), and diamide complexes, prepared from 1 and equimolar amounts of Ph_2NH, catalyzed hydrosilylation of olefins with PhSiH_3 and Ph_2SiH_2 very effectively. On the other hand, the catalysts induced dehydrogenative double silylation of conjugated dienes to give selectively 1,4-bis(silyl)-2-butenes instead of expected 1,4- and 1,2-hydrosilylation products. It has been found that hydride and silyl species, [Yb[-H and [Yb]-Si, are generated together from the catalysts and hydrosilanes and that the former reacts with the olefins and the latter with the dienes predominantly.2. Hydrophosphination of Alkynes and Related Carbon-Carbon Multiple Bonds Catalyzed by Lanthanide-Imine Complexes.Intermolecular hydrophosphination of alkynes with diphenylphosphine is catalyzed by a Yb-imine complex 1 to give alkenylphosphines and phosphine oxides after oxidative workup in good yields under mild conditions. This reaction is also applicable to various carbon-carbon multiple bonds such as conjugated diynes and dienes, allenes, and styrene derivatives. Region- and stereoselectivity, and the scope and limitation of the present reaction clearly differ from those of the corresponding radical reaction. Instead, the reaction takes place through insertion of alkynes to a Yb-PPh_2 species, followed by protonation. In fact, the Yb-phosphide complex, [Yb(PPh_2)_2(hmpa)_3], is obtained from the imine complex and phosphine, which exhibits similar catalyst activity for the hydrophosphination. The empirical rate law is v=k [catalyst]^2[alkynes]^1[phosphine]^0 at least under the standard conditions.