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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Catalytic addition of amines to carbodiimides by bis(beta-diketiminate)lanthanide(II) complexes and mechanistic studies
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Catalytic addition of amines to carbodiimides by bis(beta-diketiminate)lanthanide(II) complexes and mechanistic studies

机译：双（β-二酮化）镧系元素（II）配合物催化胺加成至碳二亚胺的机理研究

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摘要

Reduction reactions of bis(beta-diketiminate)lanthanide(III) chlorides formed in situ by reactions of anhydrous LnCl(3) with 2 equiv. of sodium salt of the beta-diketiminate ligand in THF with a Na/K alloy afforded a series of bis(beta-diketiminate) lanthanide(II) complexes LnL(2)(THF)(n) (L = L-2,L-6-Me2 = [N(2,6-Me2C6H3)C(Me)](2)CH-, n = 1, Ln = Eu (1); L = L-2,L-4,L-6-Me3 = [N(2,4,6-Me3C6H2)C(Me)](2)CH-, n = 1, Ln = Eu (2); L = L-2,L-6-iPr2 = [N(2,6-(Pr2C6H3)-Pr-i)C(Me)](2)CH-, n = 0, Ln = Eu (3), Sm (4); L = L-Ph(2,6-ipr2) = [(2,6-(Pr2C6H3)-Pr-i)NC(Me)CHC(Me)N-(C6H5)](-), n = 0, Ln = Eu (5), Yb (6); L = L2-Me = [N(2-MeC6H4)C(Me)](2)CH-, n = 1, Ln = Yb (7)) in high yields. All the complexes, especially the complexes of Sm-II (4) and Eu-II (5), were found to be excellent pre-catalysts for catalytic addition of amines to carbodiimides to multi-substituted guanidines with a wide scope of substrates. The activity depends both on the central metals and the ligands with the active sequence of Yb-II < Eu-II and Eu-II < Sm-II and L-2,L-6-Me2 < L-2,L-4,L-6-Me3 similar to L-2,L-6-iPr2 < L-Ph(2,6-ipr2) for the ligands. The mechanistic study by the isolation of guanidinate species and their reactivity revealed that EuII monoguanidinate complexes Eu(L-2,L-6-Me2)[(C6H5N)C(NHCy)(NCy)](DME) (8) and Eu(L-Ph(2,6-ipr2))[(C6H5N)C(NHCy)(NCy)](THF)(2) (9) should be the key active intermediates for the systems with Eu-II complexes and a Yb-III bis(guanidinate) complex Yb(L2-Me)[(C6H5N)C(NHCy)(NCy)](2) (11) for the system using a YbII complex.
机译：无水LnCl（3）与2当量的反应在原位形成的双（β-二酮基）镧系元素（III）氯化物的还原反应。 Na / K合金在THF中合成β-二酮基配体的钠盐，得到一系列双（β-二酮基）镧系元素（II）配合物LnL（2）（THF）（n）（L = L-2，L -6-Me2 = [N（2,6-Me2C6H3）C（Me）]（2）CH-，n = 1，Ln = Eu（1）; L = L-2，L-4，L-6- Me3 = [N（2,4,6-Me3C6H2）C（Me）]（2）CH-，n = 1，Ln = Eu（2）; L = L-2，L-6-iPr2 = [N（ 2,6-（Pr2C6H3）-Pr-i）C（Me）]（2）CH-，n = 0，Ln = Eu（3），Sm（4）; L = L-Ph（2,6-ipr2 ）= [（2,6-（Pr2C6H3）-Pr-i）NC（Me）CHC（Me）N-（C6H5）]（-），n = 0，Ln = Eu（5），Yb（6）; L = L2-Me = [N（2-MeC6H4）C（Me）]（2）CH-，n = 1，Ln = Yb（7）），收率高。发现所有络合物，特别是Sm-II（4）和Eu-II（5）的络合物都是出色的预催化剂，可将胺与碳二亚胺催化加成到具有多种底物的多取代胍上。活性取决于中心金属和配体，其活性序列为Yb-II

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