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	0000-0001-5542-9013
	1388882159

Jan Rosenboom

Phosphorus-centered radicals and biradicals

Universität Rostock, 15.08.2024

https://doi.org/10.18453/rosdok_id00005096

Abstract: This thesis deals with the synthesis, reactivity and spectroscopic properties of P-centered mono- and biradicals. First, the addition of aldehydes to the biradical [•P(μ-NTer)2P•], a classical concerted reaction mechanism, was investigated and elucidated in detail. In contrast, radical reactivity for this molecule was observed during the addition of bromoalkanes to [•P(μ-NTer)2P•]. This led to the synthesis of the persistent, phosphorus-centered monoradical [•P(μ-NTer)2PEt], which could also be detected by EPR spectroscopy as an intermediate during the radical reaction mechanism proposed here. Based on the reaction of [•P(μ-NTer)2P•] with bromoalkanes, the bridging of two biradical units was finally achieved with a dibromoalkane. From this, a phosphorus-centered disbiradical was synthesized and its special electronic situation was elucidated by means of extensive EPR experiments and quantum chemical calculations.

doctoral thesis   free access