title: Steric C-N bond activation on the dimeric macrocycle [{P(μ-NR)}2(μ-NR)]2.
abstract: Dimeric cyclophosphazanes [{P(μ-NR)}2(μ-NR)]2 [R = (t)Bu ( 1) and iPr ( 3)] were oxidized with elemental selenium. During these reactions an unexpected C–N bond cleavage and N–H bond formation occurred. Compound 1 produced P4(μ-N(t)Bu)3(μ-NH)3Se4 ( 2) where three tBu groups were lost in the form of isobutylene. In contrast, during the oxidation of the less sterically hindered 3, the resulting product, P4(μ-N(i)Pr)5(μ-NH)Se4 ( 4), showed only one substituent loss. Theoretical studies confirmed the steric nature of the driving force underlying the different outcomes.
authors.affiliation: School of Physical and Mathematical Sciences, Division of Chemistry and Biological Chemistry, Nanyang Technological University, 21 Nanyang Link, 637371, Singapore. fgarcia@ntu.edu.sg.
authors.forename: Yan X
authors.initials: YX
authors.lastname: Shi
authors.affiliation: School of Physical and Mathematical Sciences, Division of Chemistry and Biological Chemistry, Nanyang Technological University, 21 Nanyang Link, 637371, Singapore. fgarcia@ntu.edu.sg.
authors.forename: Rong Z
authors.initials: RZ
authors.lastname: Liang
authors.affiliation: School of Physical and Mathematical Sciences, Division of Chemistry and Biological Chemistry, Nanyang Technological University, 21 Nanyang Link, 637371, Singapore. fgarcia@ntu.edu.sg.
authors.forename: Katherine A
authors.initials: KA
authors.lastname: Martin
authors.affiliation: Chemistry Department, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK.
authors.forename: Daniel G
authors.initials: DG
authors.lastname: Star
authors.affiliation: Departamento de Química Orgánica e Inorgánica, Facultad de Veterinaria, Universidad de Extremadura, Cáceres 10071, Spain.
authors.forename: Jesús
authors.initials: J
authors.lastname: Díaz
authors.affiliation: School of Physical and Mathematical Sciences, Division of Chemistry and Biological Chemistry, Nanyang Technological University, 21 Nanyang Link, 637371, Singapore. fgarcia@ntu.edu.sg.
authors.forename: Xin Y
authors.initials: XY
authors.lastname: Li
authors.affiliation: School of Physical and Mathematical Sciences, Division of Chemistry and Biological Chemistry, Nanyang Technological University, 21 Nanyang Link, 637371, Singapore. fgarcia@ntu.edu.sg.
authors.forename: Rakesh
authors.initials: R
authors.lastname: Ganguly
authors.affiliation: School of Physical and Mathematical Sciences, Division of Chemistry and Biological Chemistry, Nanyang Technological University, 21 Nanyang Link, 637371, Singapore. fgarcia@ntu.edu.sg.
authors.forename: Felipe
authors.initials: F
authors.lastname: García