White Phosphorus Degradation with a NacNac Aluminum Carbene Analogue: The Biradical Reaction Mechanism

Schoeller W, Frey GD (2014)
Inorganic Chemistry 53(10): 4840-4846.

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Abstract
The title compound Al-NacNac is isolobal to the imidazol-2-ylidene (NHC); the latter is considered as a nucleophilic carbene. However, the title compound is different from a typical carbene, as aluminum is a heavier group 13 element with a predominant inert s orbital. Its singlet ground state is a poor Lewis donor (acceptor) toward white phosphorus, but its corresponding lowest energy triplet state forms a strong Al-P bond with (opened) white phosphorus. The reaction of Al-NacNac with white phosphorus proceeds in two steps: after the addition of a first carbene analogue, a second one is added, resulting in a transient biradicaloid species. This undergoes facile subsequent rearrangement, and a final ring closure reaction leads to the observed product with a bicyclobutane moiety. It is determined by intramolecular bond formation of two phosphorus centered radicals. Finally, a structure with a large singlet triplet energy separation is formed. An analogy to the noninnocent ligand character as well as the exciplex view of the monoadduct of white phosphorus with the Al-NacNac system is drawn.
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Schoeller W, Frey GD. White Phosphorus Degradation with a NacNac Aluminum Carbene Analogue: The Biradical Reaction Mechanism. Inorganic Chemistry. 2014;53(10):4840-4846.
Schoeller, W., & Frey, G. D. (2014). White Phosphorus Degradation with a NacNac Aluminum Carbene Analogue: The Biradical Reaction Mechanism. Inorganic Chemistry, 53(10), 4840-4846.
Schoeller, W., and Frey, G. D. (2014). White Phosphorus Degradation with a NacNac Aluminum Carbene Analogue: The Biradical Reaction Mechanism. Inorganic Chemistry 53, 4840-4846.
Schoeller, W., & Frey, G.D., 2014. White Phosphorus Degradation with a NacNac Aluminum Carbene Analogue: The Biradical Reaction Mechanism. Inorganic Chemistry, 53(10), p 4840-4846.
W. Schoeller and G.D. Frey, “White Phosphorus Degradation with a NacNac Aluminum Carbene Analogue: The Biradical Reaction Mechanism”, Inorganic Chemistry, vol. 53, 2014, pp. 4840-4846.
Schoeller, W., Frey, G.D.: White Phosphorus Degradation with a NacNac Aluminum Carbene Analogue: The Biradical Reaction Mechanism. Inorganic Chemistry. 53, 4840-4846 (2014).
Schoeller, Wolfgang, and Frey, Guido D. “White Phosphorus Degradation with a NacNac Aluminum Carbene Analogue: The Biradical Reaction Mechanism”. Inorganic Chemistry 53.10 (2014): 4840-4846.
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PMID: 24800980
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