title: Preparation of a diphosphine with persistent phosphinyl radical character in solution: characterization, reactivity with O2, S8, Se, Te, and P4, and electronic structure calculations.
abstract: A new, easily synthesized diphosphine based on a heterocyclic 1,3,2-diazaphospholidine framework has been prepared. Due to the large, sterically encumbering Dipp groups (Dipp = 2,6-diisopropylphenyl) on the heterocyclic ring, the diphosphine undergoes homolytic cleavage of the P-P bond in solution to form two phosphinyl radicals. The diphosphine has been reacted with O(2), S(8), Se, Te, and P(4), giving products that involve insertion of elements between the P-P bond to yield the related phosphinic acid anhydride, sulfide/disulfide, selenide, telluride, and a butterfly-type perphospha-bicyclobutadiene structure with a trans,trans-geometry. All molecules have been characterized by multinuclear NMR spectroscopy, elemental analysis, and single-crystal X-ray crystallography. Variable-temperature EPR spectroscopy was utilized to study the nature of the phosphinyl radical in solution. Electronic structure calculations were performed on a number of systems from the parent diphosphine [H(2)P](2) to amino-substituted [(H(2)N)(2)P](2) and cyclic amino-substituted [(H(2)C)(2)(NH)(2)P](2); then, bulky substituents (Ph or Dipp) were attached to the cyclic amino systems. Calculations on the isolated diphosphine at the B3LYP/6-31+G* level show that the homolytic cleavage of the P-P bond to form two phosphinyl radicals is favored over the diphosphine by ~11 kJ/mol. Furthermore, there is a significant amount of relaxation energy stored in the ligands (52.3 kJ/mol), providing a major driving force behind the homolytic cleavage of the central P-P bond.
authors.affiliation: The Maritimes Centre for Green Chemistry and the Department of Chemistry, Saint Mary's University, Halifax, Nova Scotia, Canada B3H 3C3.
authors.forename: Nick A
authors.initials: NA
authors.lastname: Giffin
authors.forename: Arthur D
authors.initials: AD
authors.lastname: Hendsbee
authors.forename: Tracey L
authors.initials: TL
authors.lastname: Roemmele
authors.forename: Michael D
authors.initials: MD
authors.lastname: Lumsden
authors.forename: Cory C
authors.initials: CC
authors.lastname: Pye
authors.forename: Jason D
authors.initials: JD
authors.lastname: Masuda