Search Results
Intermolecular hydrogen bonding in isostructural pincer complexes [OH-(t-BuPOCOPt-Bu)MCl] (M = Pd and Pt)
2019, Joksch, M., Spannenberg, A., Beweries, T.
In the crystal structure of the isostructural title compounds, namely {2,6-bis[(di-tert-butylphosphanyl)oxy]-4-hydroxyphenyl}chloridopalladium(II), [Pd(C22H39O3P2)Cl], 1, and {2,6-bis[(di-tert-butylphosphanyl)oxy]-4-hydroxyphenyl}chloridoplatinum(II), [Pt(C22H39O3P2)Cl], 2, the metal centres are coordinated in a distorted square-planar fashion by the POCOP pincer fragment and the chloride ligand. Both complexes form strong hydrogen-bonded chain structures through an interaction of the OH group in the 4-position of the aromatic POCOP backbone with the halide ligand.
Synthesis of Molybdenum Pincer Complexes and Their Application in the Catalytic Hydrogenation of Nitriles
2020, Leischner, Thomas, Spannenberg, Anke, Junge, Kathrin, Beller, Matthias
A series of molybdenum(0), (I) and (II) complexes ligated by different PNP and NNN pincer ligands were synthesized and structurally characterized. Along with previously described Mo−PNP complexes Mo-1 and Mo-2, all prepared compounds were tested in the catalytic hydrogenation of aromatic nitriles to primary amines. Among the applied catalysts, Mo-1 is particularly well suited for the hydrogenation of electron-rich benzonitriles. Additionally, two aliphatic nitriles were transformed into the desired products in 80 and 86 %, respectively. Moreover, catalytic intermediate Mo-1a was isolated and its role in the catalytic cycle was subsequently demonstrated. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
Cyclometalated Ruthenium Pincer Complexes as Catalysts for the α-Alkylation of Ketones with Alcohols
2020, Piehl, Patrick, Amuso, Roberta, Alberico, Elisabetta, Junge, Henrik, Gabriele, Bartolo, Neumann, Helfried, Beller, Matthias
Ruthenium PNP pincer complexes bearing supplementary cyclometalated C,N-bound ligands have been prepared and fully characterized for the first time. By replacing CO and H− as ancillary ligands in such complexes, additional electronic and steric modifications of this topical class of catalysts are possible. The advantages of the new catalysts are demonstrated in the general α-alkylation of ketones with alcohols following a hydrogen autotransfer protocol. Herein, various aliphatic and benzylic alcohols were applied as green alkylating agents for ketones bearing aromatic, heteroaromatic or aliphatic substituents as well as cyclic ones. Mechanistic investigations revealed that during catalysis, Ru carboxylate complexes are predominantly formed whereas neither the PNP nor the CN ligand are released from the catalyst in significant amounts. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
Cobalt-Catalyzed Aqueous Dehydrogenation of Formic Acid
2019, Zhou, Wei, Wei, Zhihong, Spannenberg, Anke, Jiao, Haijun, Junge, Kathrin, Junge, Henrik, Beller, Matthias
Among the known liquid organic hydrogen carriers, formic acid attracts increasing interest in the context of safe and reversible storage of hydrogen. Here, the first molecularly defined cobalt pincer complex is disclosed for the dehydrogenation of formic acid in aqueous medium under mild conditions. Crucial for catalytic activity is the use of the specific complex 3. Compared to related ruthenium and manganese complexes 7 and 8, this optimal cobalt complex showed improved performance. DFT computations support an innocent non-classical bifunctional outer-sphere mechanism on the triplet state potential energy surface. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.