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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
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