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Reactivity of Rare Earth Metal Alkyl Complexes with Nitriles or Isonitrile: Versatile Ways toward Multiply Functionalized β-Diketiminato, (Iso)indolyl, and Imidazolyl Chelating Rare Earth Metal Complexes
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2024-02-21 , DOI: 10.1021/acs.inorgchem.3c04079 Dianjun Guo 1 , Dongjing Hong 1 , Zeming Huang 2 , Shuangliu Zhou 1 , Xiancui Zhu 1 , Shaowu Wang 1, 2, 3
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2024-02-21 , DOI: 10.1021/acs.inorgchem.3c04079 Dianjun Guo 1 , Dongjing Hong 1 , Zeming Huang 2 , Shuangliu Zhou 1 , Xiancui Zhu 1 , Shaowu Wang 1, 2, 3
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The reactivity of the rare earth metal alkyl complexes LRE(CH2SiMe3)(THF)2 (1RE) [RE = Y (1Y), Yb (1Yb), Lu (1Lu); L = 2,5-[(2-pyrrolyl)CPh2]2(N-methylpyrrole)] with various nitriles and isonitriles has been fully developed. Treatment of the yttrium monoalkyl complex (1Y) with 2 equiv of aromatic nitriles afforded the symmetric trisubstituted β-diketiminato yttrium complexes (2Y(H), 2Y(Me), and 2Y(F)) through successive cyano group insertion into the RE–C bond and 1,3-H shift or the unsymmetric trisubstituted β-diketiminato yttrium complex (3Y) unexpectedly via a 1,3-SiMe3 shift when 4-(trifluoromethyl)benzonitrile was used in this reaction under the same conditions. By treating 1Y with 2 equiv of tolyl acetonitrile, an activation of the sp3 C–H bond occurred to form the corresponding β-aryl keteniminato complexes 4Y(p-tol) and 4Y(m-tol). Remarkably, a heteroleptic cleavage of the CO–CN bond took place in the reaction of 1Y with benzoyl nitrile, affording the unsymmetric trinuclear yttrium complex 5Y bridged by three cyanide groups. Dinuclear ytterbium and lutetium complexes 6Yb and 6Lu containing a functionalized isoindole fragment were synthesized from the reactions of 1 with phthalonitrile by tandem insertion and cyclization. Further studies indicated that the temperature and stoichiometric ratio have a great influence on the reactivity patterns between the reactions of 1RE with benzylisonitrile: two tetrasubstituted β-diketiminato complexes 8 and 9 were obtained at −30 °C, and tetrasubstituted imidazolyl yttrium and lutetium complexes 7 were isolated at elevated temperature, respectively. In addition, the tetrasubstituted β-diketiminato complexes 8 and 9 could be irreversibly converted to the cyclization products 7 by elevating the reaction temperature not only on the NMR scale but also on the preparative scale. Notably, when the phenyl isonitrile instead of benzyl isonitrile was reacted with 1Yb, a 2,3-functionalized indolyl ytterbium complex 10Yb was isolated.
中文翻译：
稀土金属烷基配合物与腈或异腈的反应性：多功能β-二酮亚胺、(异)吲哚基和咪唑基螯合稀土金属配合物的多种方法
稀土金属烷基配合物L的反应活性 RE(CH 2 SiMe 3 )(THF) 2 ( 1 RE ) [RE = Y ( 1 Y ), Yb ( 1 Yb ), Lu ( 1 Lu ); L = 2,5-[(2-吡咯基)CPh 2 ] 2 ( N-甲基吡咯)]与各种腈和异腈已得到充分开发。用 2 当量的芳香腈处理钇单烷基络合物 ( 1 Y )，通过连续的氰基插入得到对称三取代的 β-二酮亚胺钇络合物 ( 2 Y(H) 、 2 Y(Me)和2 Y(F) )当 4-(三氟甲基)苯甲腈用于此反应时，意外地通过 1,3-SiMe 3位移进入 RE-C 键和 1,3-H 位移或不对称三取代 β-二酮亚胺钇络合物 ( 3 Y )相同的条件。通过用 2 当量的甲苯基乙腈处理1 Y ， sp 3 C-H 键发生活化，形成相应的 β-芳基酮亚胺配合物4 Y( p -tol)和4 Y( m -tol) 。 值得注意的是， 1 Y与苯甲酰腈的反应中发生了 CO-CN 键的杂配断裂，得到由三个氰化物基团桥接的不对称三核钇配合物5 Y。含有功能化异吲哚片段的双核镱和镥配合物6 Yb和6 Lu是通过1与邻苯二甲腈的反应通过串联插入和环化合成的。进一步的研究表明，温度和化学计量比对1 RE与苄基异腈的反应模式有很大影响：在-30℃下得到两个四取代的β-二酮亚胺配合物8和9 ，以及四取代的咪唑基钇和镥配合物。分别在高温下分离出7个。此外，通过提高反应温度，不仅在NMR规模上而且在制备规模上，四取代的β-二酮亚胺配合物8和9可以不可逆地转化为环化产物7 。值得注意的是，当苯基异腈代替苄基异腈与1Yb反应时，分离出2,3-官能化吲哚基镱络合物10Yb 。
更新日期：2024-02-21
中文翻译：
稀土金属烷基配合物与腈或异腈的反应性：多功能β-二酮亚胺、(异)吲哚基和咪唑基螯合稀土金属配合物的多种方法
稀土金属烷基配合物L的反应活性 RE(CH 2 SiMe 3 )(THF) 2 ( 1 RE ) [RE = Y ( 1 Y ), Yb ( 1 Yb ), Lu ( 1 Lu ); L = 2,5-[(2-吡咯基)CPh 2 ] 2 ( N-甲基吡咯)]与各种腈和异腈已得到充分开发。用 2 当量的芳香腈处理钇单烷基络合物 ( 1 Y )，通过连续的氰基插入得到对称三取代的 β-二酮亚胺钇络合物 ( 2 Y(H) 、 2 Y(Me)和2 Y(F) )当 4-(三氟甲基)苯甲腈用于此反应时，意外地通过 1,3-SiMe 3位移进入 RE-C 键和 1,3-H 位移或不对称三取代 β-二酮亚胺钇络合物 ( 3 Y )相同的条件。通过用 2 当量的甲苯基乙腈处理1 Y ， sp 3 C-H 键发生活化，形成相应的 β-芳基酮亚胺配合物4 Y( p -tol)和4 Y( m -tol) 。 值得注意的是， 1 Y与苯甲酰腈的反应中发生了 CO-CN 键的杂配断裂，得到由三个氰化物基团桥接的不对称三核钇配合物5 Y。含有功能化异吲哚片段的双核镱和镥配合物6 Yb和6 Lu是通过1与邻苯二甲腈的反应通过串联插入和环化合成的。进一步的研究表明，温度和化学计量比对1 RE与苄基异腈的反应模式有很大影响：在-30℃下得到两个四取代的β-二酮亚胺配合物8和9 ，以及四取代的咪唑基钇和镥配合物。分别在高温下分离出7个。此外，通过提高反应温度，不仅在NMR规模上而且在制备规模上，四取代的β-二酮亚胺配合物8和9可以不可逆地转化为环化产物7 。值得注意的是，当苯基异腈代替苄基异腈与1Yb反应时，分离出2,3-官能化吲哚基镱络合物10Yb 。
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