325982-75-0Relevant academic research and scientific papers
Behavior of group 6 fischer aminocarbene complexes in a supercharged medium: A single electron transfer-H atom transfer process
Lage, Marta L.,Mancheno, Maria J.,Martinez-Alvarez, Roberto,Gomez-Gallego, Mar,Fernandez, Israel,Sierra, Miguel A.
, p. 2762 - 2772 (2009)
The ESI-MS study of the ionization of a series of aryl, alkenyl, and alkynyl (Fischer) aminocarbene complexes is described. The process requires the initial capture of one electron from the ESI source, followed by the transfer of a hydrogen atom to the additive (TTF or Cs2CO3). Regardless of their structure, both NH and N,N-disubstituted aminocarbenes can effectively ionize under ESI-MS conditions, as long as they have abstractable H atoms. Overall, the process can be envisaged as a single electron transfer-H atom transfer process. The experimental findings are supported by DFT calculations. The ESI-MS ionization of bis-alkynylaminocarbene complexes follows the same patterns. However, the [M - H]- ions evolve by arylacetylene extrusion together with the usual sequence of CO loss. The process requires the presence of a free NH group and occurs by intramolecular hydrogen transfer from the NH to the metal center. Bis-aminocarbenes having rigid tethers between the nitrogen atoms or lacking free NH groups do not produce this fragmentation.
Reaction of alkynyl alkoxy metal carbene complexes with 1,2-diamines
Moreto, Josep M.,Ricart, Susagna,Doetz, Karl Heinz,Molins, Elies
, p. 62 - 70 (2008/10/08)
Reaction of alkynyl alkoxy carbenes 1 with 1,2-primary and secondary diamines is discussed. The descriptions of mono and biscarbene amino complexes and the effect of the reaction conditions, esteric and electronic factors on the product distribution are also discussed. Changes in the reaction conditions were found to effect greatly the resulting products.
