Applications of transition metal complexes containing 3,3?-bis(diphenylphosphinoamine)-2,2?-bipyridine ligand to transfer hydrogenation of ketones
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Tarih
2012
Yazarlar
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
Elsevier Science Sa
Erişim Hakkı
info:eu-repo/semantics/closedAccess
Özet
Hydrogen transfer reduction processes are attracting increasing interest from synthetic chemists in view of their operational simplicity. 3,3'-bis(diphenylphosphinoamine)-2,2'-bipyridine, (Ph2PNH)(2)C10H6N2, was prepared through a single step reaction of 3,3'-diamino-2,2'-bipyridine with diphenyl-chlorophosphine. Reaction of (Ph2PNH)(2)C10H6N2 with [Ru(eta(6)-benzene)(mu-Cl)Cl](2), [Rh(mu-Cl)(cod)](2) or [Ir(eta(5)-C5Me5)(mu-Cl)Cl](2) gave a range of new bridged dinuclear complexes (C10H6N2{NHPPh2Ru(eta(6)-benzene)Cl-2}(2)], 1, [C10H6N2{PPh2NHRh(cod)Cl}(2)], 2 and [C10H6N2{NHPPh2Ir(eta(5)-C5Me5)Cl-2}(2)], 3, respectively. All new complexes have been fully characterized by analytical and spectroscopic methods. (HP)-H-1-P-31{H-1} NMR, (HC)-H-1-C-13 HETCOR or (HH)-H-1-H-1 COSY correlation experiments were used to confirm the spectral assignments. 1, 2 and 3 are suitable catalyst precursors for the transfer hydrogenation of acetophenone derivatives. Notably [Ru((Ph2PNH)(2)C10H6N2)(eta(6)-benzene)Cl-2], 1 acts as an excellent catalyst, giving the corresponding alcohols in 98-99% yields in 10 min at 82 degrees C (TOF <= 600 h(-1)) for the transfer hydrogenation reaction in comparison to analogous rhodium or iridium complexes. This transfer hydrogenation is characterized by low reversibility under these conditions. (C) 2012 Elsevier B.V. All rights reserved.
Açıklama
Anahtar Kelimeler
Aminophosphine, Transition Metal, Transfer Hydrogenation, Catalyst, Nmr
Kaynak
Journal of Organometallic Chemistry
WoS Q Değeri
Q2
Scopus Q Değeri
Q2
Cilt
720
