0000000000505249
AUTHOR
Timo Gans-eichler
N-Heterocyclic Phosphenium, Arsenium, and Stibenium Ions as Ligands in Transition Metal Complexes: A Comparative Experimental and Computational Study
Reaction of 2-chloro-1,3,2-diazaarsolenes and -diazaphospholenes with Tl[Co(CO)4] gives instable complexes of type [Co(ER2)(CO)4] which decarbonylated to yield [Co(ER2)(CO)3]. Spectroscopic and X-ray diffraction studies revealed that the tetracarbonyl complexes can be formulated as ion pair for E = P and as covalent metalla-arsine for E = As, and the tricarbonyl complexes as carbene-like species with a formal E=Co double bond. A similar reactivity towards Tl[Co(CO)4] was also inferred for 1,3,2-diazastibolenes although the products were not isolable and their constitution remained uncertain. Evaluation of structural and computational data suggests that the weak and polarized Co–As bond in […
The transfer of tin and germanium atoms from N-heterocyclic stannylenes and germylenes to diazadienes.
New N-heterocyclic stannylenes and germylenes were synthesized by transamination of E[N(SiMe3)2] (E = Ge, Sn) with alpha-amino-aldimines or ethylidene-1,2-diamines and were characterized by spectroscopic methods and in the case of the germylene 10 g by X-ray diffraction. The reactions of several germylenes and stannylenes with diazadienes were studied by using dynamic NMR and computational methods. Experimental and theoretical studies confirmed that metathesis with exchange of the Group 14 atom is feasible for both stannylenes and germylenes, with exchange rates being generally higher for stannylenes. The metathesis of the diazadiene 3 b and the stannylene 1 b follows second-order kinetics …