Details

Autor(en) / Beteiligte

• Koner, Abhishek
• Gabidullin, Bulat M
• Kelemen, Zsolt
• Nyulászi, László
• Nikonov, Georgii I
• Streubel, Rainer

Titel

7-Metalla-1,4-diphosphanorbornadienes: cycloaddition of monovalent group 13 NacNac complexes to a stable 1,4-diphosphinine

Ist Teil von

• Dalton transactions : an international journal of inorganic chemistry, 2019-06, Vol.48 (23), p.8248-8253

Ort / Verlag

England: Royal Society of Chemistry

Erscheinungsjahr

2019

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• This work presents the first example of a dienophilic property of the monovalent group-13 NacNac complexes, which are well-known for their carbene-like reactivity, e.g. , addition to multiple bonds, insertion into single bonds, and oxidative cleavage of some multiple bonds. In reactions with imidazole-2-thione based tricyclic 1,4-diphospinine 4 , the monovalent compounds NacNacM (M = Al,Ga) showed dienophilic behaviour and produced the corresponding 7-metalla-1,4-diphosphanorbornadienes ( 5-6 ), leaving the C&z.dbd;S functionality of the imidazole-2-thione intact, while the NacNacIn complex did not show any reactivity because of unfavourable thermodynamics. DFT calculations revealed that for NacNacAl, the cycloaddition was kinetically more favoured (due to a small reaction barrier) than the oxidative cleavage of the C&z.dbd;S functionality, despite the fact that the product of the C&z.dbd;S bond addition has a somewhat higher stability. For NacNacGa, the cycloaddition reaction was both kinetically and thermodynamically favourable than the cleavage of C&z.dbd;S. Furthermore, these reactions were found to be reversible in nature and diphosphinine 4 showed a clear preference towards Al than towards Ga which reflects the better inclination of Ga to stay monovalent than be in the trivalent state. Monovalent group 13 NacNac complexes reacted as dienophiles with a tricyclic 1,4-diphosphinine to furnish first examples of 7-metalla-1,4-diphosphanorbornadienes via reversible [4 + 1]-cycloaddition reactions.