Reaktionen von Metallcarbonylen mit Aziridin

Abstract

Die Hexacarbonyle von Chrom, Molybdan und Wolfram setzen sich photochemisch oder thermisch mit Aziridin (in) zu Komplexcn M(CO)fj-,in, (n = I, 2, 3) um. Aus den cis-Bis(aziridin)tctracarbonylmetall-Verbindungen entstehen in Gegcnwart von protischen Losungsmittelii durch Reaktion zwischen zwei Aziridinliganden Tetracarbonylkomplexe M(C0)ddiin mit dem N-(2-Aminoathyl)aziridin-Chelatligandcn (dun). Aus Tc-CH3C-HdMn(C0)3 und in bzw. diin werdeii die Verbindungen x-CH3C:~H~Mn(CO)~in bzw. (x-CH3CsH4)-(CO)2Mn~-diin-Mn(CO)2(n-CH+Z5H4) erhalten. Die Struktur-und Bindungsverhaltnisse in diesen Komplexcri werden an Hand der IR-Spektren diskutiert. Reactions of Metal Carbonyls with AziridineThe photochemical or thermal reaction of the hexacarbonyls of chromium, molybdenum, and tungsten with aziridine (in) yields the complexes M(CO)6-ninn (n -1, 2, 3). From the cisbis(aziridin)tetracarbonylmetal compounds in the presence of protic solvents chelate complexes M(C0j4diin with N-(2-aminoethyl)aziridine (diin) as ligdnd, formed by rcaction of two aziridine ligands, have been obtained. The preparation of n-CH3CsFI1Mn(CO)zin and of (Tc-CH3C5H4)(C0)2Mn-diin-Mn(CO)2(sr-CH3CSF14) is rcported. The structure and bonding of these complexes arc discussed on the basis of the i. r. spectra. Mit Aziridin sind bereits eine Reihe von kationischen Metallkomplexenz) desTyps [M(in),Im I (M z. B. = Ag 1, Ni2+; in = Aziridin) bekannt. Vor kurzeni untersuchten Fritz und Hierl3) auf Grund von IR-und NMR-Messungen die Bindungsverhaltnisse in diesen Komplexen. Bei der Wmsetzung von Pentacarbonyl(methoxy-methy1carben)chrom mit Isonitrilen bildet sich ein Carbenkomplex mit ALiridinstruktur". Octacarbonyldikobalt setd sich mit Aziridin unter Valenzdisproportionierung des Metalls zu [Coins] [Co(CO)4]2 urns). Vor kurzem berichteten wir uber die Reaktion von Carbonylmetallhydriden mit Ariridin, die unter Ringoffnung des Aziridins zu /3-Aminopropionylchelat-Komplexen fiihrt 1). Wir untersuchten nun die Umsetzungen von Aziridin mit verschiedenen neutralen Metallcarbonylen. 1 ) 2. Mitteil. Uber Reaktionen +on Metallkomplexen mil gespannten Ringsystcmen; 1.

Synthesis of chiral 1-(2-aminoalkyl)aziridines via the self-opening reaction of aziridine

“…However, this reaction has been described in only a few papers and concerns specific reactions, namely, the synthesis of complexes of aziridines with transition metals. Transition metal (Cr, Mo, W, Cd, Co)-mediated ring-opening reactions of aziridine ligands yielding aminoethylaziridine-N,N′ complexes by 'aziridine dimerization' were first observed by Beck 24 and Fritz 25 and then by others. 26,27 Recently, synthesis, X-ray structural characterization, antimicrobial and cytotoxic effects of aziridine and 1-(2-aminoethyl)aziridine complexes of Cu(II) and Pd(II) have been reported.…”

Synthesis, structural characterization, antimicrobial and cytotoxic effects of aziridine, 2-aminoethylaziridine and azirine complexes of copper(ii) and palladium(ii)

“…The 49 but without any structural characterization. Beck et al also observed the first "aziridine dimerization" induced by metal coordination.…”

“…with hydrido carbonyl complexes to form β-aminoacyl complexes via M-C addition [42][43][44][45][46] or with halogenido carbonyl complexes to form five-membered aminooxycarbene complexes. 47,48 Transition metal-mediated ring opening reactions of aziridine ligands yielding aminoethylaziridine-N,N′ complexes by "aziridine dimerization" was first observed by Beck et al 49 and Fritz et al 50 The first examples of such an aziridine dimer template have been structurally characterized by X-ray determination in the case of a cationic Co(III) complex bearing two dimerized 2-methylaziridine ligands. 51 We later reported further examples of analogous complexes with dimerized aziridine ligands.…”

“…51 We later reported further examples of analogous complexes with dimerized aziridine ligands. 52,53 Furthermore, most recently a novel route to N-(2-aminoethyl)aziridines was developed based on the one reported by Beck et al 49 utilizing a Cu(II)-mediated template dimerization of aziridine ligands. 53 In this paper we report on the synthesis and characterization of new palladium(II) and copper(II) complexes with dimerized aziridine ligands as well as of palladium(II) complexes with one N-bound aziridine ligand and two azirine ligands, respectively.…”

, der erste einzähnig koordinierte Aziridin-Komplex / , the First Mono-Coordinate Aziridine Complex

“…Beck et cd. haben schon früher die R eaktivität von A ziridinen ge genüber M etallcarbonylen untersucht [5]. Sie ha ben vor allem RingÖffnungsreaktionen beobachtet.…”