%0 Journal Article
%A Bowden, Allen
%A Coles, Simon
J.
%A Pitak, Mateusz B.
%A W. G. Platt, Andrew
%D 2012
%T Complexes of Lanthanide
Nitrates with Tri Tert Butylphosphine
Oxide
%U https://acs.figshare.com/articles/journal_contribution/Complexes_of_Lanthanide_Nitrates_with_Tri_Tert_Butylphosphine_Oxide/2536018
%R 10.1021/ic300142r.s002
%2 https://ndownloader.figshare.com/files/4179025
%K abundance isomer
%K Lanthanide Nitrates
%K Variable temperature
%K Tri Tert Butylphosphine OxideReaction
%K NMR spectrum
%K structures show L
%K nitrate ligands coplanar
%K temperature solution 31 P NMR measurements
%K cationic species
%K unit cell
%K lanthanide nitrates
%K nitrate ligands
%K Ln
%K Lu
%K 3PO
%K 31 P
%K bipyramidal geometry
%X Reaction of lanthanide nitrates with tBu3PO (=L) lead to the isolation of complexes Ln(NO3)3L2·H2O·nEtOH
(Ln = La (1), Nd(2)), Ln(NO3)3L2 ·nEtOH (Sm(3), Eu(4)), and Ln(NO3)3L2 (Dy(5), Er(6), Lu(7)). These have been characterized by elemental analysis, infrared
and NMR(1H, 13C and 31P) spectroscopy
and single-crystal X-ray diffraction. The structures show L to be
positioned on opposite sides of the metal with the nitrates forming
an equatorial band. When Ln = Dy, Er, and Lu two distinct molecules
are present in the unit cell. A major isomer (70%) has a (P)O–Ln–O(P)
angle of less than 180° with one of the nitrate ligands twisted
out of the plane of the other nitrates while the lower abundance isomer
is more symmetric with the (P)O–Ln–O(P) angle of 180°
and the nitrate ligands coplanar giving a hexagonal bipyramidal geometry.
These isomers cannot be observed by variable temperature solution 31P NMR measurements but are clearly seen in the solid-state
NMR spectrum of the Lu complex. Variable temperature solid-state NMR
indicates that the isomers do not interconvert at temperatures up
to 100 °C. Attempts to prepare cationic species [Ln(NO3)2L3]+[PF6]− have not been totally successful and led to the isolation of crystals
of Lu(NO3)3L2 and Tb(NO3)3L2.CH3CN (8).
%I ACS Publications