Neue Übergangsmetallkomplexe mit Nuclein‐Basen und Nucleosiden

Abstract

Die Darstellung von Carbonylmetallkomplexen W(CO)5L (l), [W(CO),L]-(Z), [ M O ( C O )~~~L ] ~ (3), (x-CH3C5H4)Mn(CO)zL (4), Rh(CO),(Cl)L (51 I~(HXCOXPP~~)ZL~ (6), M(COMPPhd& (M = Rh, Ir) (7,8) und von phosphin-und amin-haltigen monomeren sowie mehrkernigen Palladium(I1)-und Platin(I1)-Komplexen (9 -14) mit einer Reihe von neutralen und anionischen Purinund Pyrirnidin-Basen und Nucleosiden L wird beschrieben. Mit Hilfe von IR-und 'H-NMR-Daten wird versucht, die Koordinationsstellen der ambidenten Nucleinbasen zu bestimmen. 1,3,7,9-Tetramethylxanthinium-perchlorat wird mit Quecksilber(I1)-acetat am C-8 metalliert (15). New Transition Metal Complexes with Nucleic Acid Bases and Nucleosides The isolation of carbonylmetal complexes W(CO)5L (I), [W(CO),L]-(2), [Mo(CO),enL]-(3), (x-CH3C5H4)Mn(C0)2L (4), Rh(CO),(CI)L (51 Ir(HXCO)(PPh3)2L2 (6) M(CO)(PPh3)zL (M = Rh, Ir) (7, 8), and of phosphine and amine containing monomeric and polynuclear palladium(I1) and platinum(I1) complexes (9 -14) with various neutral and anionic nucleic acid bases and nucleosides L is reported. Using i. r. and 'H n. m. r. data a tentative assignment of the coordination sites of the ambidentate ligands is given. The reaction of 1,3,7,9-tetramethylxanthinium perchlorate with Hg" acetate d o r d s the C-8 mercurated complex 15.Bis vor wenigen Jahren war das komplexchemische Verhalten der Purinund Pyridinbasen nur sporadisch untersucht worden ' 3 '). Neue Impulse erhielt die Chemie der Metallkomplexe rnit Nucleinbasen erst durch den Nachweis der biologischen Aktivitat von Schwermetall-Anionen a d DNS ' ) und durch die Entdeckung der cancerostatischen Wirkung von cis-Diaminplatin(II>Verbindungen 4). Eine Reihe von Arbeitskreisen befal3t sich in neuerer Zeit rnit der Isolierung 3, ~ ' ) und der spektroskopischen Charakterisierung

Metal ion biomolecule interactions. PART VII. Synthesis, spectroscopic properties and crystal structure investigations of some bis(theophyllinato)tetraaquocadmium(II) compounds

“…Similar strong bands, attributed to the 6(H20) mode and the two C = O stretching vibrations found at -1685 and -1635 cm-', have been found in a number of complexes containing the theophyllinate ion (5,36). Free theophylline has corresponding absorptions at 1720 and 1680 cm-' .…”

Organometallic Complexes of Uracil and Orotic Acid Derivatives: Coordination Mode, Structure, and Reactivity

“…The ν(CO) vibrational modes and 13 C NMR chemical shifts for the carbonyl ligands of complexes 1 and 3 indicate that the metal centers are more electron-rich than those of complex 2. This conclusion is further substantiated by the rates of intermolecular CO exchange in these carbonylmetal anions with 13 CO. The facile CO exchange observed in complexes 1 and 3 is faster than that seen in complex 2.…”

“…[11,12] Despite the plethora of coordination complexes of pyrimidines, the organometallic chemistry involving these ligands has received limited attention, with most efforts coming from the laboratory of Beck and co-workers. [13,14] Recently, we have examined the coordination modes of uracils and orotic acid derivatives to zero-valent group-6 carbonylmetal compounds, focusing our studies on the ability of the ring nitrogen atoms to serve as π-donor ligands and to facilitate CO dissociation. [15,16] Previously, investigations of the coordination chemistry of uracils have revealed a wide range of metal-dependent binding modes, including via N1, N3, the exocyclic oxygen atoms, [1,2] both an endocyclic nitrogen and an exocyclic oxygen (or sulfur) atom, [15,17] and finally, though less common, through C5.…”

A Novel Field of Research: Bioorganometallic Chemistry, Origins, and Founding Principles

“…Chapters 5 and 6 give additional examples of organometallic peptides and proteins with chemical, biochemical and biological aims. Among the first organometallic complexes with nucleobases was a series of metal carbonyl complexes with these bioligands [220][221][222]. The structures of nucleobase-bridged carbonyl rhodium complexes were determined by Sheldrick [223], who also obtained a series of half-sandwich ruthenium complexes with nucleobases (Scheme 1.25) [224][225][226].…”