Die Hydrido‐Komplexe RuHCl(CO)(PPh3)3, RuH2(PPh3)4 und IrH3(PPh3)3 reagieren mit N‐Acyl‐α‐Amino‐carbonsäuren unter Bildung der Carboxylat‐Komplexe RuCl(O2CCHRNHCOR′)(CO)(PPh3)2 (1–3), RuH(O2CCHRNHCOR′)(PPh3)3 (4–6) und IrH2(O2CCH2NHCOPh)(PPh3)3 (7). Die Struktur von RuCl(O2CCH2NHCOPh)(CO)(PPh3)2 (1) wurde röntgenographisch bestimmt. Phosphan‐Komplexe der Formel MBr(O2CCH2NHCOR)(CO)2(PPh3)2 (M = Mo, W) (8–12) und Mo(O2CCHRNHCOR′)2(CO)2(PPh3)2 (13–17) entstehen bei der Umsetzung von MBr2(CO)2(PPh3)2 mit einem bzw. zwei Äquivalenten N‐Acyl‐α‐Aminocarboxylat‐Anionen.
2-Fluorophenyl Glycine and Alanine, 2-Thienyl Glycine and Alanine, Ruthenium o-Fluorophenyl glycine and alanine, 2-thienyl glycine and alanine form with dinuclear, chloro bridged metal complexes the chiral N, O-chelates (arene)M (Cl)(NH2C H R C 0 2) (M = Ru, Rh, Ir; arene = cymene, Cp*) and (R3P)(C1)M(NH2C H R C 0 2) (M = Pd, Pt) as mixtures of diastereoisomers or cis/trans-isomers, respectively.
Durch Umsetzung von chloroverbrückten Verbindungen mit Sarkosinat, N‐Methylalaninat und Ethylendiamin‐N, N′‐diacetat wurden die Halbsandwich‐Chelat‐Komplexe [Cp*M(Cl)(NHMeCHRCO2)] (M = Ir, Rh; R = H, Me), [(p‐Cymol)Ru(Cl)(NHMeCHRCO2)] (R = H, Me) mit chiralen Metall‐ und N‐Atomen, die Palladium‐ und Platin‐Komplexe [(R3P)(Cl)M(NHMeCHR′CO2)] (M = Pd, Pt; R′ = H, Me) sowie die zweikernigen Komplexe [(Cl)(R3P)M(O2CCH2NHCH2CH2NHCH2CO2)M(PR3)(Cl)] erhalten. Die bei diesen Komplexen möglichen Diastereomeren werden anhand der 1H‐, 13C‐ und 31P‐NMR‐Daten diskutiert.
β-Phenylalanine forms with chloro bridged complexes the chiral N, O-chelates Cp*Ir(Cl)(NH2CH(Ph)CH2CO2) and (p-cymene)Ru(Cl)(NH2CHPhCH2CO2) as mixture of two diastereoisomers. Similarly the palladium(III) and platinum(II) complexes (Et3P)(Cl)M(NH2CH(Ph)CH2CO2) (M = Pd, Pt) were obtained. Schiff base complexes (arene)(Cl)M(O2CC(R)=N-CH(R)CH(R)CH2CO2CH3) (arene = Cp*, p-cymene; M = Ir, Ru) were synthesized from the chloro-bridged compounds, 2-oxocarboxylates and β-alanine or β-phenylalanine methylester. The Cp*Ir complex with a tridendate dianionic Schiff base generated from pyruvate and β-phenylalaninate is obtained as a single isomer. Cp*Ir(Cl) forms a complex with an N, O-bidentate Schiff base ligand from glycinate and acetylacetic ethyl ester.
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