A comparison of 4f vs 5f metal-metal bonds in (CpSiMe3)3M-ECp* (M = Nd, U; E = Al, Ga; Cp* = C5Me5): synthesis, thermodynamics, magnetism, and electronic structure.
Reaction of (CpSiMe(3))(3)U or (CpSiMe(3))(3)Nd with (Cp*Al)(4) or Cp*Ga (Cp* = C(5)Me(5)) afforded the isostructural complexes (CpSiMe(3))(3)M-ECp* (M = U, E = Al (1); M = U, E = Ga (2); M = Nd, E = Al (3); M = Nd, E = Ga (4)). In the case of 1 and 2 the complexes were isolated in 39 and 90% yields, respectively, as crystalline solids and were characterized by single-crystal X-ray diffraction, variable-temperature (1)H NMR spectroscopy, elemental analysis, variable-temperature magnetic susceptibility, and UV-visible-NIR spectroscopy. In the case of 3 and 4, the complexes were observed by variable-temperature (1)H NMR spectroscopy but were not isolated as pure materials. Comparison of the equilibrium constants and thermodynamic parameters DeltaH and DeltaS obtained by (1)H NMR titration methods revealed a much stronger U-Ga interaction in 2 than the Nd-Ga interaction in 4. Competition reactions between (CpSiMe(3))(3)U and (CpSiMe(3))(3)Nd indicate that Cp*Ga selectively binds U over Nd in a 93:7 ratio at 19 degrees C and 96:4 at -33 degrees C. For 1 and 3, comparison of (1)H NMR peak intensities suggests that Cp*Al also achieves excellent U(III)/Nd(III) selectivity at 21 degrees C. The solution electronic spectra and solid-state temperature-dependent magnetic susceptibilities of 1 and 2, in addition to X-ray absorption near-edge structure (XANES) measurements from scanning transmission X-ray microscopy (STXM) of 1, are consistent with those observed for other U(III) coordination complexes. DFT calculations using five different functionals were performed on the model complexes Cp(3)M-ECp (M = Nd, U; E = Al, Ga), and empirical fitting of the values for Cp(3)M-ECp allowed the prediction of binding energy estimates for Cp*Al compounds 1 and 3. NBO/NLMO bonding analyses on Cp(3)U-ECp indicate that the bonding consists predominantly of a E-->U sigma-interaction arising from favorable overlap between the diffuse ligand lone pair and the primarily 7s/6d acceptor orbitals on U(III), with negligible U-->E pi-donation. The overall experimental and computational bonding analysis suggests that Cp*Al and Cp*Ga behave as good sigma-donors in these systems.
Minasian
Stefan G
SG
Department of Chemistry, University of California, Berkeley, California 94720, USA.
Krinsky
Jamin L
JL
Rinehart
Jeffrey D
JD
Copping
Roy
R
Tyliszczak
Tolek
T
Janousch
Markus
M
Shuh
David K
DK
Arnold
John
J