5624-60-2Relevant articles and documents
Synthesis and Structures of Bis(indolyl)-Coordinated Titanium Dichlorido Complexes and Their Catalytic Application in the Cyclotrimerization of Alkynes
Itoh, Keigo,Miura, Narumi,Miyamoto, Ryo,Ohta, Shun,Okazaki, Masaaki,Saitoh, Keiichiro,Satoh, Sora
, p. 2826 - 2835 (2021/09/02)
The impact of the terminal ligands on the titanium center on the coordination features of deprotonated 2,2′-bis(indolyl)methanes (henceforth: bis(indolyl)s) was studied via a structural comparison between {bis(indolyl)}Ti(NEt2)2 complexes and the corresponding dichlorido complexes. As a result, several flexible aspects of bis(indolyl) coordination were found. For example, it was revealed that an η1-coordinated indolyl moiety can change its coordination mode to coordination via the five-membered ring of indolyl when the terminal diethylamido ligands are replaced by chlorido ligands. Moreover, we found that the methoxy group in the central aromatic ring of the bis(indolyl) ligand can coordinate to the titanium center. The synthesized dichlorido complexes were applied for catalytic alkyne cyclotrimerization reactions, as Ti-based catalyst systems are less developed than Co-, Ni-, Ru-, Rh-, and Ir-based systems. During this study, the cyclotrimerization of HCCSiMe3 was found to preferentially produce the 1,3,5-form (1,3,5-form:1,2,4-form = 79:21), contrary to the typical trend of transition-metal-mediated alkyne cyclotrimerization, and the isolated yield (72%) is the highest among the known 1,3,5-favoring reactions using Ti-based catalyst systems. Furthermore, the reaction mechanism was experimentally verified to proceed through a typical stepwise mechanism involving monomeric species.
Synthesis of a highly crystalline, covalently linked porous network
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Page/Page column 3; 13, (2019/05/15)
Porous networks are described linked by boronates. Also described are processes for producing the porous networks. The porous networks are formed by reacting a polyboronic acid with itself or with a polydiol, a polydiamine, or a polyamino alcohol. The res
Cyclotrimerization of alkynes catalyzed by a self-supported cyclic tri-nuclear nickel(0) complex with α-diimine ligands
Shen, Lingyi,Zhao, Yanxia,Luo, Qiong,Li, Qian-Shu,Liu, Bin,Redshaw, Carl,Wu, Biao,Yang, Xiao-Juan
supporting information, p. 4643 - 4649 (2019/04/05)
A cyclic tri-nuclear α-diimine nickel(0) complex [{Ni(μ-LMe-2,4)}3] (2) was synthesized from a “pre-organized”, trimerized trigonal LNiBr2-type precursor [Ni3(μ2-Br)3(μ3-Br)2(LMe-2,4)3]·Br (1; LMe-2,4 = [(2,4-Me2C6H3)NC(Me)]2). In complex 2, the α-diimine ligands not only exhibit the normal N,N′-chelating mode, but they also act as bridges between the Ni atoms through an unusual π-coordination of a C═N bond to Ni. Complex 2 is able to catalyze the cyclotrimerization of alkynes to form substituted benzenes in good yield and regio-selectivity for the 1,3,5-isomers, which is found to vary with the nature of the alkyne employed. This complex represents a convenient self-supported nickel(0) catalyst with no need for additional ligands and reducing agent.