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Synthesis, Structure, and Ammonia Oxidation Catalytic Activity of Ru-NH3 Complexes Containing Multidentate Polypyridyl Ligands
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2021-09-07 , DOI: 10.1021/acs.inorgchem.1c01528 Jan Holub 1 , Nataliia Vereshchuk 1, 2 , Francisco-Javier Sánchez-Baygual 1 , Marcos Gil-Sepulcre 1 , Jordi Benet-Buchholz 1 , Antoni Llobet 1, 3
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2021-09-07 , DOI: 10.1021/acs.inorgchem.1c01528 Jan Holub 1 , Nataliia Vereshchuk 1, 2 , Francisco-Javier Sánchez-Baygual 1 , Marcos Gil-Sepulcre 1 , Jordi Benet-Buchholz 1 , Antoni Llobet 1, 3
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Ammonia (electro)oxidation with molecular catalysts is a rapidly developing topic with wide practical applications ahead. We report here the catalytic ammonia oxidation reaction (AOR) activity using [Ru(tda-κ-N3O)(py)2], 2, (tda2– is 2,2′:6′,2′′-terpyridine-6,6′′-dicarboxylate; py is pyridine) as a catalyst precursor. Furthermore, we also describe the rich chemistry associated with the reaction of Ru-tda and Ru-tPa (tPa–4 is 2,2′:6′,2′′-terpyridine-6,6′′-diphosphonate) complexes with NH3 and N2H4 using [RuII(tda-κ-N3O)(dmso)Cl] (dmso is dimethyl sulfoxide) and [RuII(tPa-κ-N3O)(py)2], 8, as synthetic intermediates, respectively. All the new complexes obtained here were characterized spectroscopically by means of UV–vis and NMR. In addition, a crystal X-ray diffraction analysis was performed for complexes trans-[RuII(tda-κ-N3)(py)2(NH3)], 4, trans-[RuII(tda-κ-N3)(N-NH2)(py)2], 5, cis-[RuII(tda-κ-N3)(py)(NH3)2], 6 (30%), and cis-[RuII(tda-k-N3)(dmso)(NH3)2], 7 (70%). The AOR activity associated with 2 and 8 as catalyst precursors was studied in organic and aqueous media. For 2, turnover numbers of 7.5 were achieved under bulk electrolysis conditions at an Eapp = 1.4 V versus normal hydrogen electrode in acetonitrile. A catalytic cycle is proposed based on electrochemical and kinetic evidence.
中文翻译：
含多齿多吡啶配体的 Ru-NH3 配合物的合成、结构和氨氧化催化活性
用分子催化剂进行氨（电）氧化是一个快速发展的课题，具有广泛的实际应用前景。我们在此报告了使用 [Ru(tda-κ-N 3 O)(py) 2 ], 2 , (tda 2–是 2,2':6',2''-三联吡啶-6,6''-二羧酸盐；py 是吡啶）作为催化剂前体。此外，我们还描述了与 Ru-tda 和 Ru-tPa（tPa –4是 2,2':6',2''-terpyridine-6,6''-diphosphonate）配合物与 NH反应相关的丰富化学反应3和 N 2 H 4使用 [Ru II (tda-κ-N 3 O)(dmso)Cl]（dmso 是二甲亚砜）和 [Ru II(tPa-κ-N 3 O)(py) 2 ], 8分别作为合成中间体。这里获得的所有新配合物都通过紫外-可见光和核磁共振进行光谱表征。此外，还对反式-[Ru II (tda-κ-N 3 )(py) 2 (NH 3 )], 4 ,反式-[Ru II (tda-κ-N 3 )(N-NH 2 )(py) 2 ], 5 ,顺-[Ru II (tda-κ-N 3 )(py)(NH 3 )2 ]、6 (30%)和顺式-[Ru II (tda-kN 3 )(dmso)(NH 3 ) 2 ]、7 (70%)。在有机和水介质中研究了与2和8作为催化剂前体相关的 AOR 活性。对于2，在E app = 1.4 V 的本体电解条件下，相对于乙腈中的普通氢电极，实现了 7.5 的转换数。基于电化学和动力学证据提出了催化循环。
更新日期：2021-09-20
中文翻译：
含多齿多吡啶配体的 Ru-NH3 配合物的合成、结构和氨氧化催化活性
用分子催化剂进行氨（电）氧化是一个快速发展的课题，具有广泛的实际应用前景。我们在此报告了使用 [Ru(tda-κ-N 3 O)(py) 2 ], 2 , (tda 2–是 2,2':6',2''-三联吡啶-6,6''-二羧酸盐；py 是吡啶）作为催化剂前体。此外，我们还描述了与 Ru-tda 和 Ru-tPa（tPa –4是 2,2':6',2''-terpyridine-6,6''-diphosphonate）配合物与 NH反应相关的丰富化学反应3和 N 2 H 4使用 [Ru II (tda-κ-N 3 O)(dmso)Cl]（dmso 是二甲亚砜）和 [Ru II(tPa-κ-N 3 O)(py) 2 ], 8分别作为合成中间体。这里获得的所有新配合物都通过紫外-可见光和核磁共振进行光谱表征。此外，还对反式-[Ru II (tda-κ-N 3 )(py) 2 (NH 3 )], 4 ,反式-[Ru II (tda-κ-N 3 )(N-NH 2 )(py) 2 ], 5 ,顺-[Ru II (tda-κ-N 3 )(py)(NH 3 )2 ]、6 (30%)和顺式-[Ru II (tda-kN 3 )(dmso)(NH 3 ) 2 ]、7 (70%)。在有机和水介质中研究了与2和8作为催化剂前体相关的 AOR 活性。对于2，在E app = 1.4 V 的本体电解条件下，相对于乙腈中的普通氢电极，实现了 7.5 的转换数。基于电化学和动力学证据提出了催化循环。
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