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Structurally characterized dipalladium(ii)-oxamate metallacyclophanes as efficient catalysts for sustainable Heck and Suzuki reactions in ionic liquids†‡
Inorganic Chemistry Frontiers ( IF 7 ) Pub Date : 2018-07-04 00:00:00 , DOI: 10.1039/c8qi00498f Francisco Ramón Fortea-Pérez 1, 2, 3, 4, 5 , Mouly Lahcen El Idrissi Moubtassim 6, 7, 8, 9, 10 , Donatella Armentano 11, 12, 13, 14 , Giovanni De Munno 11, 12, 13, 14 , Miguel Julve 1, 2, 3, 4, 5 , Salah-Eddine Stiriba 1, 2, 3, 4, 5
Inorganic Chemistry Frontiers ( IF 7 ) Pub Date : 2018-07-04 00:00:00 , DOI: 10.1039/c8qi00498f Francisco Ramón Fortea-Pérez 1, 2, 3, 4, 5 , Mouly Lahcen El Idrissi Moubtassim 6, 7, 8, 9, 10 , Donatella Armentano 11, 12, 13, 14 , Giovanni De Munno 11, 12, 13, 14 , Miguel Julve 1, 2, 3, 4, 5 , Salah-Eddine Stiriba 1, 2, 3, 4, 5
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A new generation of dipalladium-oxamate metallacyclophanes of formulas (n-NBu4)4 [Pd2(ppba)2] (1), (n-NBu4)4[Pd2(dpvba)2] (2), (n-NBu4)4[Pd2(dpazba)2] (3), (n-NBu4)4[Pd2(dpeba)2] (4) and (n-NBu4)4[Pd2(tpeba)2] (5) [n-NBu4+ = tetra-n-butylammonium cation, H4ppba = N,N′-1,4-phenylenebis(oxamic acid), H4dpvba = N,N′-4,4′-diphenylethenebis(oxamic acid), H4dpazba = N,N′-4,4′-diphenylazobis(oxamic acid), H4dpeba = N,N′-4,4′-diphenylethynebis(oxamic acid) and H4tpeba = N,N′-1,4-di(4-phenylethynyl)phenylenebis(oxamic acid)] was prepared. The crystal structure of the solvated species of 2–4, namely (n-NBu4)4[Pd2(dpvba)2]·6MeOH·2Et2O (2a), (n-NBu4)4[Pd2(dpazba)2]·8MeOH (3a), and (n-NBu4)2[Pd2(dpeba)2]·8MeOH (4a), was determined by single crystal X-ray diffraction. These compounds crystallize in the triclinic space group P(![[1 with combining macron]](https://www.rsc.org/images/entities/char_0031_0304.gif)
) and they have in common the presence of tetraanionic dipalladium(II) units corresponding to [3,3] metallacyclophane-type motifs connected by two N–Pd–N bonds. Each palladium(II) ion in 2a–4a is a four-coordinate ion with two carboxylate-oxygen and two amidate-nitrogen atoms of two fully deprotonated oxamate fragments from two bis(oxamate) ligands building a square planar surrounding, which forms a loop oligomer. The bis(oxamate) ligands exhibit a syn (trans, trans) arrangement. Because of their ionic character, the catalytic potential of dipalladium(II) compounds 1–5 was investigated for both Heck and Suzuki coupling reactions in several ionic liquids. Our results show that they are very efficient and robust catalysts, catalyzing the carbon–carbon bond forming reaction of iodoaryl with phenylboronic acid and ethyl acrylate in short times at the melting reaction temperature of n-Bu4NBr used as a molten salt reaction medium. They remain active after at least six successive runs, without significant reductions in yields at 120 °C.
中文翻译：
结构上具有特征性的二铝钯（ii）-草酸酯金属环烷酮是离子液体中可持续的Heck和Suzuki反应的有效催化剂† ‡
新一代式为（n -NBu 4）4 [Pd 2（ppba）2 ]（1），（n -NBu 4）4 [Pd 2（dpvba）2 ]（2），（n -NBu 4）4 [Pd 2（dpazba）2 ]（3），（n -NBu 4）4 [Pd 2（dpeba）2 ]（4）和（n -NBu4） 4 [钯2（tpeba） 2 ]（ 5）[ Ñ -nBu 4 + =四Ñ -butylammonium阳离子，H 4 PPBA = Ñ， Ñ '-1,4-亚苯基二（草氨酸），H 4 dpvba = ñ， ñ '-4,4'- diphenylethenebis（草氨酸），H 4 dpazba = ñ， ñ '-4,4'- diphenylazobis（草氨酸），H 4 dpeba = ñ， ñ '-4,4' -二苯基乙炔二（草酰胺酸）和H 4 tpeba = N，Ñ '-1,4-二（4-苯基乙炔基）苯基双（草氨酸）]的制备。的溶剂化物质的晶体结构2-4，即（Ñ -nBu 4）4 [钯2（dpvba）2 ]·6MeOH·2ET 2 O（2A），（Ñ -nBu 4）4 [钯2（dpazba ）2 ]·8MeOH（3a）和（n -NBu 4）2 [Pd 2（dpeba）2 ]·8MeOH（4a）是通过单晶X射线衍射测定的。这些化合物在三斜晶系空间群P（）中结晶，并共同存在四阴离子二钯（II）单元，该单元对应于通过两个N–Pd–N键连接的[3,3]金属环烷型基序。2a–4a中的每个钯（II）离子都是四配位离子，带有两个完全去质子化的草酸酯碎片的两个羧酸氧原子和两个酰胺化氮原子，来自两个双（草酸酯）配体，构成一个正方形平面周围，形成一个环低聚物。双（草酸酯）配体表现出syn（反式，反式） 安排。由于它们的离子特性，对几种离子液体中的Heck和Suzuki偶联反应均研究了二钯（II）化合物1-5的催化潜力。我们的结果表明，它们是非常有效且坚固的催化剂，在用作熔融盐反应介质的n -Bu 4 NBr的熔融反应温度下，可在短时间内催化碘代芳基与苯基硼酸和丙烯酸乙酯的碳-碳键形成反应。它们至少连续运行六次后仍保持活性，而在120°C下收率没有明显降低。
更新日期：2018-07-04
) and they have in common the presence of tetraanionic dipalladium(II) units corresponding to [3,3] metallacyclophane-type motifs connected by two N–Pd–N bonds. Each palladium(II) ion in 2a–4a is a four-coordinate ion with two carboxylate-oxygen and two amidate-nitrogen atoms of two fully deprotonated oxamate fragments from two bis(oxamate) ligands building a square planar surrounding, which forms a loop oligomer. The bis(oxamate) ligands exhibit a syn (trans, trans) arrangement. Because of their ionic character, the catalytic potential of dipalladium(II) compounds 1–5 was investigated for both Heck and Suzuki coupling reactions in several ionic liquids. Our results show that they are very efficient and robust catalysts, catalyzing the carbon–carbon bond forming reaction of iodoaryl with phenylboronic acid and ethyl acrylate in short times at the melting reaction temperature of n-Bu4NBr used as a molten salt reaction medium. They remain active after at least six successive runs, without significant reductions in yields at 120 °C.
中文翻译：
结构上具有特征性的二铝钯（ii）-草酸酯金属环烷酮是离子液体中可持续的Heck和Suzuki反应的有效催化剂† ‡
新一代式为（n -NBu 4）4 [Pd 2（ppba）2 ]（1），（n -NBu 4）4 [Pd 2（dpvba）2 ]（2），（n -NBu 4）4 [Pd 2（dpazba）2 ]（3），（n -NBu 4）4 [Pd 2（dpeba）2 ]（4）和（n -NBu4） 4 [钯2（tpeba） 2 ]（ 5）[ Ñ -nBu 4 + =四Ñ -butylammonium阳离子，H 4 PPBA = Ñ， Ñ '-1,4-亚苯基二（草氨酸），H 4 dpvba = ñ， ñ '-4,4'- diphenylethenebis（草氨酸），H 4 dpazba = ñ， ñ '-4,4'- diphenylazobis（草氨酸），H 4 dpeba = ñ， ñ '-4,4' -二苯基乙炔二（草酰胺酸）和H 4 tpeba = N，Ñ '-1,4-二（4-苯基乙炔基）苯基双（草氨酸）]的制备。的溶剂化物质的晶体结构2-4，即（Ñ -nBu 4）4 [钯2（dpvba）2 ]·6MeOH·2ET 2 O（2A），（Ñ -nBu 4）4 [钯2（dpazba ）2 ]·8MeOH（3a）和（n -NBu 4）2 [Pd 2（dpeba）2 ]·8MeOH（4a）是通过单晶X射线衍射测定的。这些化合物在三斜晶系空间群P（
）中结晶，并共同存在四阴离子二钯（II）单元，该单元对应于通过两个N–Pd–N键连接的[3,3]金属环烷型基序。2a–4a中的每个钯（II）离子都是四配位离子，带有两个完全去质子化的草酸酯碎片的两个羧酸氧原子和两个酰胺化氮原子，来自两个双（草酸酯）配体，构成一个正方形平面周围，形成一个环低聚物。双（草酸酯）配体表现出syn（反式，反式） 安排。由于它们的离子特性，对几种离子液体中的Heck和Suzuki偶联反应均研究了二钯（II）化合物1-5的催化潜力。我们的结果表明，它们是非常有效且坚固的催化剂，在用作熔融盐反应介质的n -Bu 4 NBr的熔融反应温度下，可在短时间内催化碘代芳基与苯基硼酸和丙烯酸乙酯的碳-碳键形成反应。它们至少连续运行六次后仍保持活性，而在120°C下收率没有明显降低。
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