Neutrale Bis‐Aziridin‐Komplexe des Typs [M(CO)₃XAz₂] (M = Mn, Re; X = Cl, Br; Az = N(H)C₂H₂Me₂)

Abstract

In einer thermisch induzierten Substitutionsreaktion mit 2,2‐Dimethylaziridin lassen sich die Pentacarbonyl‐Halogeno‐Komplexe [XM(CO)5] (M = Mn, Re; X = Cl, Br) (1a – 2b) zu den neutralen Bis‐Aziridin‐Komplexen [M(X)(CO)3Az2] (Az = N(H)C2H2Me2) (3a – 4b) umsetzen. Den Röntgenstrukturanalysen zufolge sind die Metallatome oktaedrisch in facialer Anordnung konfiguriert; die intakten Dreiringe sind über die verzerrt tetraedrisch konfigurierten N‐Atome gebunden. Verbindungen 3a – 4b sind hinsichtlich einer gezielten Alken‐Abspaltung unter Bildung von Nitren‐Komplexen stabil; ihre IR‐, 1H‐ und 13C{1H}‐NMR‐ und MS‐Spektren werden vorgestellt und diskutiert.

Reactivity of 2,2-dimethylaziridine towards d10 transition metal halides

“…Due to the excess az released in the reaction solution by light induced decomposition of 9, nucleophilic attack on the az ligands of 9 occurs yielding formation of the [(aiaz)HgI 2 ] complex. CÀC and CÀN bond lengths and angles differ only marginally from those found for other transition metal coordinated aiaz ligands [20][21][22]. HgÀNH 2 R, HgÀNR 3 and HgÀI bond lengths of 2.387(6) Å , 2.346(7) Å and 2.7139(9) Å , 2.6683(10) Å observed for 10 are comparable with the bond lengths described for similar 1,2-diaminoethanemercury(II)iodide complexes, but compared to 8 the difference between the Hg-NR 3 and the HgÀNH 2 R bond lengths is smaller [45].…”

“…The zinc(II) center in 6 is coordinated by two bromido ligands and the nitrogens of two aziridines resulting in a slightly distorted tetrahedral geometry. Selected bond angles and bond lengths of 6 together with the molecular structure are given in figure 1 angles differ slightly from those of the free aziridine 1 in the solid state [39] and only marginally from those found for other 3-D transition metal coordinated aziridines [20][21][22]. Both ZnÀN and ZnÀBr bond lengths of 2.018(4) and 2.019(4) or 2.3717(9) and 2.4192(8) observed in 6 are in good agreement with the bond lengths described for comparable zinc(II)-sec.-amine compounds [40].…”

“…Hieber and Wiesboeck [10] introduced the aziridine ligand in organometallic chemistry by reacting it with [Co 2 (CO) 8 ] yielding [Co (C 2 H 5 N) 6 ] 2þ [CoðCOÞ À 4 ] 2 . Subsequently, the coordination chemistry of aziridines has been widely explored [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25]. As expected for secondary and tertiary amine ligands, the coordination chemistry of aziridines shows the preference for metal coordination by the N atom.…”

2H-Azirines as ligands: Synthesis and structural characterization of (2H-3-arene-azirine)ReI(CO)3Br complexes

“…The ReÀligand bond lengths in 4a-d lie within the expected ranges. Re-C CO and Re-Br bond lengths are comparable to those in similar Re I (CO) 3 L 2 Br complexes [29]. The average value for the Re(1)-Br(1) bonds is 2.599(1) Å and those for the Re(1)-C CO bonds lie within the range of 1.92(1) Å and 2.01(1) Å.…”

“…Obviously the azirine ligands act as r-donorp-donor ligands and favour the double bond of the p-acceptor CO in trans position. The Re-N sp2 bond lengths are shortened with 2.150 Å for Re(1)ÀN(1) and 2.145 Å for Re(1)ÀN(2) (4a) compared to analogous aziridine complexes with Re-N sp3 2.199 Å and 2.202 Å [29]. Further bond lengths and angles of 4a-d are listed in Table 1.…”