New Functional Cyclic Aminomethylphosphine Ligands for the Construction of Catalysts for Electrochemical Hydrogen Transformations |
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| Authors: | Dr Elvira I Musina Vera V Khrizanforova Igor D Strelnik Murad I Valitov Yulia S Spiridonova Dr Dmitry B Krivolapov Dr Igor A Litvinov Dr Marsil K Kadirov Dr Peter Lönnecke Prof?Dr Evamarie Hey‐Hawkins Prof?Dr Yulia H Budnikova Prof?Dr Andrey A Karasik Prof?Dr Oleg G Sinyashin |
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| Institution: | 1. A.?E. Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Sciences, Kazan Scientific Center, Arbuzov str. 8, 420088 Kazan (Russian Federation), Fax: (+7)?8432752253;2. Institut für Anorganische Chemie, Universit?t Leipzig, Johannisallee 29, 04103 Leipzig (Germany) |
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| Abstract: | Eight‐membered cyclic functional bisphosphines, namely 1,5‐di‐aryl‐3,7‐di(2‐pyridyl)‐1,5‐diaza‐3,7‐diphosphacyclooctanes (aryl=2‐pyridyl, m‐tolyl, p‐tolyl, diphenylmethyl, benzyl, (R)‐(+)‐(α‐methyl)benzyl), with 2‐pyridyl substituents on the phosphorus atoms have been synthesized by condensation of 2‐pyridylphosphine, formaldehyde, and the corresponding primary amine. The structures of some of these bisphosphines have been investigated by X‐ray crystallography. The bisphosphines readily form neutral P,P‐chelate complexes (κ2‐P,P‐L)MCl2], cationic bis‐P,P‐chelate complexes (κ2‐P,P‐L)2M]2+, or a five‐coordinate complex (κ2‐P,P‐L)2NiBr]Br. The electrochemical behavior of two of the nickel complexes, and their catalytic activities in electrochemical hydrogen evolution and hydrogen oxidation, including the fuel‐cell test, have been studied. |
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| Keywords: | diazadiphosphacyclooctanes electrochemistry hydrogen metal complexes pyridylphosphines |
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