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Remote Substituent Effects on the Structures and Stabilities of P═E π-Stabilized Diphosphatetrylenes (R 2 P) 2 E (E = Ge, Sn)

DOI: 10.1021/acs.inorgchem.6b01566 DOI Help

Authors: Keith Izod (Newcastle University) , Peter Evans (Newcastle University) , Paul Waddell (Newcastle University) , Mike Probert (Newcastle University)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Inorganic Chemistry , VOL 55 , PAGES 10510 - 10522

State: Published (Approved)
Published: October 2016
Diamond Proposal Number(s): 6749

Abstract: A rare P–E π interaction between the lone pair of a planar P center and the vacant p orbital at the Ge or Sn center provides efficient stabilization for P-substituted tetrylenes (R2P)2E (E = Ge, Sn) and enables isolation of the first example of a compound with a crystallographically authenticated P═Sn bond. Subtle changes in the electronic properties of the bulky aryl substituents in these compounds change the preference for planar versus pyramidal P centers in the solid state; however, variable-temperature NMR spectroscopy indicates that in solution these species are subject to a dynamic equilibrium, which interconverts the planar and pyramidal P centers. Consistent with this, density functional theory studies suggest that there is only a small energy difference between the planar and pyramidal forms of these compounds and reveal a small singlet–triplet energy separation, suggesting potentially interesting reactivities.

Subject Areas: Chemistry

Instruments: I19-Small Molecule Single Crystal Diffraction