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Issue 23, 2019
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7-Metalla-1,4-diphosphanorbornadienes: cycloaddition of monovalent group 13 NacNac complexes to a stable 1,4-diphosphinine

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Abstract

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[double bond, length as m-dash]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[double bond, length as m-dash]S functionality, despite the fact that the product of the C[double bond, length as m-dash]S bond addition has a somewhat higher stability. For NacNacGa, the cycloaddition reaction was both kinetically and thermodynamically favourable than the cleavage of C[double bond, length as m-dash]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.

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

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Publication details

The article was received on 04 Apr 2019, accepted on 29 Apr 2019 and first published on 16 May 2019


Article type: Paper
DOI: 10.1039/C9DT01425J
Dalton Trans., 2019,48, 8248-8253

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

    A. Koner, B. M. Gabidullin, Z. Kelemen, L. Nyulászi, G. I. Nikonov and R. Streubel, Dalton Trans., 2019, 48, 8248
    DOI: 10.1039/C9DT01425J

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