Weerachai Silprakob, Jannatul Ferdous, Sanjit Das, Jonah W. Jurss, Elizabeth T. Papish
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引用次数: 0
摘要
由 N-杂环碳化物 (NHC) 和吡啶环组成的 CNC 钌钳形复合物是高活性的二氧化碳还原催化剂。我们假设,在这些 CNC 钳子上添加具有烯烃末端的长链脂肪族基团作为翼尖,可以通过闭环偏聚反应(RCM)形成大环催化剂。我们合成了三种含有长链烯烃翼尖(吡啶环上 N 的对位取代基为 H、Me 或 OMe)的新型钌钳形催化剂 [(CNC)Ru(CH3CN)2Cl]OTf,并对一种 R = Me 的化合物进行了 RCM 反应,随后进行了氢化反应,形成了一种新型大环钌催化剂。在有外部光敏剂(敏化)和无外部光敏剂(自敏化)的情况下,对这四种催化剂进行了光催化还原二氧化碳(CO2)的测试。在有光敏剂的情况下,这些催化剂主要产生 CO(775 至 1210 吨),也会产生少量 H2。甲基取代的大环催化剂在 72 小时内产生的一氧化碳吨数为 1185 吨,而类似的非大环催化剂产生的一氧化碳吨数为 775 吨。在 R = OMe > H ≈ Me 的情况下,吡啶中心环的对位上的远位取代基对催化剂活性有显著影响。
Synthesis, Characterization, and Catalytic CO2 Reduction Reactivity of Ruthenium CNC Pincer Complexes Containing Macrocyclic or Long Chain Wingtips
Ruthenium CNC pincer complexes, comprised of N-heterocyclic carbenes (NHCs) and a pyridyl ring, are highly active catalysts for carbon dioxide reduction. We hypothesized that the addition of long chain aliphatic groups with an olefin terminus as wingtips on these CNC pincers could be used to form macrocyclic catalysts by ring closing metathesis (RCM). We have synthesized three new ruthenium pincer catalysts, [(CNC)Ru(CH3CN)2Cl]OTf, containing a long chain olefin wingtip (where the substituent para to N on the pyridine ring is H, Me, or OMe) and performed RCM on one compound with R = Me, followed by hydrogenation, to form a novel macrocyclic ruthenium catalyst. These four catalysts were tested for the photocatalytic reduction of carbon dioxide (CO2) in the presence (sensitized) and absence (self-sensitized) of an external photosensitizer. With a photosensitizer, these catalysts produced mostly CO (775 to 1210 TON) with smaller amounts of H2 also formed. The methyl substituted macrocyclic catalyst showed a TON of 1185 for CO over 72 h compared to a TON of 775 for CO for the analogous nonmacrocyclic catalyst. The remote substituents at the para-position of the central pyridine ring significantly influence catalyst activity with R = OMe > H ≈ Me.
期刊介绍:
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.