title: Reversible, photoinduced activation of P₄ by low-coordinate main group compounds.
abstract: Two unique systems based on low-coordinate main group elements that activate P4 are shown to quantitatively release the phosphorus cage upon short exposure to UV light. This reactivity marks the first reversible reactivity of P4, and the germanium system can be cycled 5 times without appreciable loss in activity. Theoretical calculations reveal that the LUMO is antibonding with respect to the main group element-phosphorus bonds and bonding with respect to reforming the P4 tetrahedron, providing a rationale for this unprecedented activity, and suggesting that the process is tunable based on the substituents.
authors.affiliation: Department of Chemistry and Center for Advanced Materials and Biomaterials Research (CAMBR), The University of Western Ontario, 1151 Richmond St., N6A 5B7 London, Ontario (Canada), Fax: (+1) 519-661-3022.
authors.forename: Jonathan W
authors.initials: JW
authors.lastname: Dube
authors.forename: Cameron M E
authors.initials: CM
authors.lastname: Graham
authors.forename: Charles L B
authors.initials: CL
authors.lastname: Macdonald
authors.forename: Zachary D
authors.initials: ZD
authors.lastname: Brown
authors.forename: Philip P
authors.initials: PP
authors.lastname: Power
authors.forename: Paul J
authors.initials: PJ
authors.lastname: Ragogna
keywords: bond activation; germanium; main group chemistry; reversible reactivity; white phosphorus