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首页> 外文期刊>Organometallics >DFT study of olefin versus nitrogen bonding in the coordination of nitrogen-containing polar monomers to diimine and salicylaldiminato nickel(II) and palladium(II) complexes. Implications for copolymerization of olefins with nitrogen-containing polar
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DFT study of olefin versus nitrogen bonding in the coordination of nitrogen-containing polar monomers to diimine and salicylaldiminato nickel(II) and palladium(II) complexes. Implications for copolymerization of olefins with nitrogen-containing polar

机译：DFT研究烯烃与氮键在含氮极性单体与二亚胺和水杨基亚氨基镍（II）和钯（II）配合物中的配位作用。烯烃与含氮极性共聚的意义

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An initial screening of late-transition-metal catalysts and nitrogen-containing polar monomers toward an incorporation of amines or nitriles in the polymer chain of polyolefins has been performed using density functional theory. Substrates of the type CH2=CH(CH2)(n)X (X = polar group) can bind either with the N-containing polar group or with the pi moiety to the metal center of the catalyst. Monomer-catalyst combinations favoring the pi complex over the N complex are promising, because the pi-binding mode can subsequently lead to polymer growth. The stabilization energies for the pi and N complexes of monomers of the type CH2=CH(CH2)(n)CN, CH2=CH(CH2)(n)NH2, and CH2=CH(CH2)(n)N(CH3)(2) with generic models for the recently reported nickel(II) and palladium(II) catalysts with diimine ("Brookhart") and salicylaldiminato ("Grubbs") ligands have been calculated. While the investigated polar monomers have been shown to form very strong metal-nitrogen bonds with the Brookhart nickel catalysts, the enamine prefers the pi binding mode in its complexes with all model catalysts. Promising results have also been obtained for the coordination of nitriles and amines with the Grubbs nickel catalysts. The palladium systems show an even larger preference for pi coordination than their nickel counterparts. An energy-decomposition scheme has been used to rationalize the relative strength of the catalyst-monomer bonds. [References: 55]
机译：使用密度泛函理论已经初步筛选了过渡金属催化剂和含氮极性单体，以便在聚烯烃的聚合物链中引入胺或腈。 CH2 = CH（CH2）（n）X（X =极性基团）类型的底物可以与含N的极性基团或与pi部分结合到催化剂的金属中心。比π络合物更倾向于π络合物的单体-催化剂组合是有前途的，因为pi结合模式可以随后导致聚合物的生长。 CH2 = CH（CH2）（n）CN，CH2 = CH（CH2）（n）NH2和CH2 = CH（CH2）（n）N（CH3）类型的单体的pi和N配合物的稳定能（2）用最近报告的具有二亚胺（“ Brookhart”）和水杨基亚氨基（“ Grubbs”）配体的镍（II）和钯（II）催化剂的通用模型进行了计算。尽管已证明所研究的极性单体可与Brookhart镍催化剂形成非常强的金属-氮键，但烯胺在其与所有模型催化剂的配合物中均更喜欢pi结合模式。在腈和胺与格拉布斯镍催化剂的配位方面也取得了令人鼓舞的结果。与镍相比，钯体系对π配位的偏好更大。已经使用能量分解方案来合理化催化剂-单体键的相对强度。 [参考：55]

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