Heteroleptic alkyl and amide iminoanilide alkaline earth and divalent rare earth complexes for the catalysis of hydrophosphination and (cyclo)hydroamination reactions.
Heteroleptic alkyl and amide iminoanilide alkaline earth and divalent rare earth complexes for the catalysis of hydrophosphination and (cyclo)hydroamination reactions.
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DOI：
10.1002/chem.201301464
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发表时间：
2013-09
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影响因子：
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通讯作者：
Bo Liu;T. Roisnel;J. Carpentier;Y. Sarazin
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文献类型：
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作者：
Bo Liu;T. Roisnel;J. Carpentier;Y. Sarazin
提出了带有亚氨基苯胺配体 ({N^N}(-)) 的碱土金属 (M=Ca, Sr, Ba) 和二价稀土金属 (Yb(II) 和 Eu(II) ) 的 [{N^N}M(X)(thf)n] 烷基 (X=CH(SiMe3)2) 和酰胺 (X=N(SiMe3)2) 配合物。值得注意的是，这些配合物被证明在溶液中是动力学稳定的。 X 射线衍射研究使我们能够确定尺寸结构趋势。除一例[{N^N}Yb(II){N(SiMe3)2}(thf)]氧化外，所有这些配合物在催化条件下都很稳定，是末端氨基烯烃环氢胺化以及活化烯烃分子间氢胺化和分子间氢膦化的有效预催化剂。碱土金属和稀土金属族中具有相同尺寸的金属表现出几乎相同的表观催化活性和选择性。烃基配合物是比其酰胺类似物更好的催化剂前体。在环氢胺化的情况下，表观活性随着金属尺寸的增加而降低：Ca>Sr>Ba，动力学速率定律符合R(CHA) =k[预催化剂](1)[氨基烯烃](1)。苯乙烯的分子间氢氨化和氢膦酸化具有反马尔可夫尼科夫区域特异性。在这两种情况下，表观活性都随着离子半径的增加而增加（Ca<Sr<Ba），但速率定律不同，并且分别服从R(HA)=k[苯乙烯](1)[胺](1)[预催化剂](1)和R(HP)=k[苯乙烯](1)[HPPh2](0)[预催化剂](1)。提出了与速率定律和动力学同位素效应兼容的机制。 [{N^N}Ba{N(SiMe3)2}(thf)2] (3) 和 [{N^N}Ba{CH(SiMe3)2}(thf)2] (10) 是第一个用于分子间氢胺化和氢膦化的高效 Ba 基预催化剂，其活性值高于迄今为止报道的值。详细介绍了预催化剂形成 C-N 和 C-P 键的潜力，并提出了罕见的环氢胺化-分子间氢胺化“多米诺骨牌”序列。
[{N^N}M(X)(thf)n] alkyl (X=CH(SiMe3)2) and amide (X=N(SiMe3)2) complexes of alkaline earths (M=Ca, Sr, Ba) and divalent rare earths (Yb(II) and Eu(II) ) bearing an iminoanilide ligand ({N^N}(-)) are presented. Remarkably, these complexes proved to be kinetically stable in solution. X-ray diffraction studies allowed us to establish size-structure trends. Except for one case of oxidation with [{N^N}Yb(II){N(SiMe3)2}(thf)], all these complexes are stable under the catalytic conditions and constitute effective precatalysts for the cyclohydroamination of terminal aminoalkenes and the intermolecular hydroamination and intermolecular hydrophosphination of activated alkenes. Metals with equal sizes across alkaline earth and rare earth families display almost identical apparent catalytic activity and selectivity. Hydrocarbyl complexes are much better catalyst precursors than their amido analogues. In the case of cyclohydroamination, the apparent activity decreases with metal size: Ca>Sr>Ba, and the kinetic rate law agrees with R(CHA) =k[precatalyst](1)[aminoalkene](1). The intermolecular hydroamination and hydrophosphination of styrene are anti-Markovnikov regiospecific. In both cases, the apparent activity increases with the ionic radius (Ca<Sr<Ba) but the rate laws are different, and obey R(HA) =k[styrene](1)[amine](1)[precatalyst](1) and R(HP) =k[styrene](1)[HPPh2 ](0)[precatalyst](1), respectively. Mechanisms compatible with the rate laws and kinetic isotopic effects are proposed. [{N^N}Ba{N(SiMe3)2}(thf)2] (3) and [{N^N}Ba{CH(SiMe3)2}(thf)2] (10) are the first efficient Ba-based precatalysts for intermolecular hydroamination and hydrophosphination, and display activity values that are above those reported so far. The potential of the precatalysts for C-N and C-P bond formation is detailed and a rare cyclohydroamination-intermolecular hydroamination "domino" sequence is presented.