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New chiral C2-symmetric bis(phosphinite) ligands containing imine group were synthesized from 1-({[(1R,2R)-2-{[(2-hydroxynaphthalen-1-yl)methylidene] amino}cyclohexyl]- imino}methyl)- naphthalen-2-ol and two equivalents of Ph2PCl, (i-Pr)2PCl or (Cy)2PCl, in high yields. Binuclear C2-symmetric half sandwich η6-p-cymene-Ru(II) complexes of the chiral phosphinite ligands were synthesized by treating of [Ru(η6-p-cymene)(μ-Cl)Cl]2 with the phosphinites in 1:1 M ratio in CH2Cl2. Their catalytic activities in asymmetric transfer hydrogenation (ATH) were investigated for the reaction of acetophenone derivatives with isopropyl alcohol. The corresponding optically active secondary alcohols were obtained in excellent levels of conversion (96–99%) and moderate enantioselectivity (up to 60% ee). Among three complexes investigated, complex 4 was the most efficient one.

The combination of [3-[(2S)-2-[(diphenylphosphanyl)oxy]-3-phenoxypropyl]-1-methyl-1H-imidazol-3-ium chloride] with [Ru(eta(6)-arene)(mu-Cl)Cl](2), Ir(eta(5)-C5Me5)(mu-Cl)Cl](2) or [Rh(mu-Cl)(cod)](2), in the presence of KOH/isoPrOH, has been found to generate catalysts that are capable of enantioselectively reducing alkyl, aryl ketones to the corresponding (R)-alcohols. Under optimized conditions, when the catalysts were applied to the asymmetric transfer hydrogenation, we obtained the secondary alcohol products in high conversions and enantioselectivities using only 0.5 mol% catalyst loading. In addition, [3-[(2S)-2-{[(chloro(eta(4)-1,5-cyclooctadiene)rhodium)diphenyl phosphanyl] oxy}-3-phenoxypropyl]-1-methyl-1H-imidazol-3-ium chloride], (6) complex is much more active than the other analogous complexes in the transfer hydrogenation. Catalyst 6 acts as excellent catalysts, giving the corresponding (R)-1-phenyl ethanol in 99% conversion in 30 min (TOF

P-N bağı içeren ligandların sentezi bu tür ligandlar üzerinden değişik yapılara ulaşmak mümkün olduğundan oldukça ilgi çekmektedir. Bis(fosfino)aminler de organometalik kimyada, katalizde ve anti kanser araştırmalarında kullanıldıkları için önem kazanmışlardır. Bis(fosfino)aminler arasında bis(difenilfosfino)anilin türevleri sentezlerinin kolay olması ve aminofosfinlere göre genellikle daha kararlı olduklarından araştırmalarda yaygın olarak kullanılan bileşiklerdendir. Bu nedenle ticari olarak bulunan anilin türevlerinden birçok bis(difenilfosfino)anilin bileşiği sentezlenmiş ve reaktiflikleri araştırılmıştır. P-N bağına aldehit yada keton katılmasıyla α-aminofosfonat denilen katılma ürünleri meydana gelir. Bu α-aminofosfonatlar birçok antibakteriyel, antiviral ve antifungal aktif olan α-aminofosfonik asit türevinin sentezinde anahtar konumda olduklarından biyolojik yönden önemlidir. Bu çalışmada yeni bis(fosfino)amin ligandları, bunların kalkojenleri ve birkaç geçiş metal (Pt, Pd ve bazen Cu, Ni) kompleksleri hazırlandı. Bis(fosfino)aminler ayrıca aldehit veya ketonlarla etkileştirilerek α-aminofosfonat katılma ürünleri elde edilmeye çalışıldı. Sentezlenen bileşiklerin yapıları IR ve NMR spektroskopisi, element analizi ve tek kristal yapısı elde edilenlerin yapıları X ışınları difraksiyonuyla aydınlatıldı. Anahtar Kelimeler Fosfor (III) ligandı, metoksianilin, bis(fosfino)amin, katılma, aldehit, keton, α- aminofosfonat The synthesis and coordination chemistry of phosphorus(III) ligands containing P-N linkages have received widespread attention. Potentially this ligand family is quite attractive since preparative routes enable access to various structural modifications via simple P-N bond formation. In this context, bis(phosphino)amines have attracted considerable interest in recent years as they are used in organometallic chemistry and catalysis as well as in anticancer researches. Among the bis(phosphino)amines, the bis(diphenylphosphino)aniline derivatives are the most frequently used precursors in investigations because of their facile synthesis and relatively high stability. Starting from the commercially available aniline derivatives, a large number of bis(diphenylphosphino)anilines have been prepared and their reactivities have been investigated. Insertion of aldehydes or ketones into the P-N bond leads to the formation of α- aminophosphonates. These inserted products are biologically important as they are the key precursors for synthesizing numerous antibacterial, antiviral and antifungal active α-aminophosphonic acid derivatives. Present study describes the synthesis of new bis(phosphino)amines and their chalcogen derivatives as well as several transition metal (Pt, Pd in some cases Cu, Ni) complexes. Furthermore, the bis(phoshino)amines were reacted with some aldehydes or ketones to afford inserted products. All new compounds were characterized by microanalysis, IR, NMR spectroscopy and in several cases by X-ray crystallography. Key Words Phosphorous(III) ligand, methoxyaniline, bis(phoshino)amine, aldehyde, ketone, insertion, α-aminophosphonate

Chiral ruthenium catalyst systems generated in situ from [Ru(eta(6)-p-cymene)(mu-Cl)Cl](2) complex and chiral C-2-symmetric bis(phosphinite) ligands based on amino alcohol derivatives were employed in the asymmetric transfer hydrogenation of aromatic ketones to give the corresponding optically active alcohols in high yield. The best results were obtained in the [Ru(eta(6)-p-cymene)(mu-Cl)Cl](2) and (2S)-2-[benzyl(2-{benzyl[(2S)-1-[(diphenylphosphanyl)oxy]-3-phenyl propan-2-yl]amino}ethyl)amino]-3-phenylpropyl diphenylphosphinite or (2R)-2-[benzyl(2-{benzyl[(2R)-1-[(diphenylphosphanyl) oxy]-3-phenylpropan-2-yl]amino}ethyl) amino]-3-phenylpropyl diphenylphosphinite catalytic systems, which gave enantioselectivities of up to 93% ee and 99% conversion.