Organometallic ruthenium, rhodium and iridium complexes containing a P-bound thiophene-2-(N-diphenylphosphino)methylamine ligand: Synthesis, molecular structure and catalytic activity

2011-07-01
AYDEMİR, MURAT
BAYSAL, AKIN
MERİÇ, NERMİN
KAYAN, CEZMİ
Gumgum, Bahattin
Özkar, Saim
ŞAHİN, Ertan
Reaction of Ph2PNHCH2-C4H3S with [Ru(eta(6)-p-cymene)(mu-Cl)Cl](2), [Ru(eta(6)-benzene)(mu-Cl)Cl](2), [Rh(mu-Cl)(cod)](2) and [Ir(eta(5)-C5Me5)(mu-Cl)Cl](2) yields complexes [Ru(Ph2PNHCH2-C4H3S)(eta(6)-p-cymene)Cl-2], 1, [Ru(Ph2PNHCH2-C4H3S)(eta(6)-benzene)Cl-2], 2, [Rh(Ph2PNHCH2-C4H3S)(cod)Cl], 3 and [Ir(Ph2PNHCH2-C4H3S)(eta(5)-C5Me5)Cl-2], 4, respectively. All complexes were isolated from the reaction solution and fully characterized by analytical and spectroscopic methods. The structure of [Ru(Ph2PNHCH2-C4H3S)(eta(6)-benzene)Cl-2], 2 was also determined by single crystal X-ray diffraction. 1-4 are suitable precursors forming highly active catalyst in the transfer hydrogenation of a variety of simple ketones. Notably, the catalysts obtained by using the ruthenium complexes [Ru(Ph2PNHCH2-C4H3S)(eta(6)-p-cymene)Cl-2], 1 and [Ru(Ph2PNHCH2-C4H3S)(eta(6)-benzene)Cl-2], 2 are much more active in the transfer hydrogenation converting the carbonyls to the corresponding alcohols in 98-99% yields (TOF <= 200 h(-1)) in comparison to analogous rhodium and iridium complexes.