title: Highly Fluxional [Y(C(SiH(CH3)2)3)3]: A DFT Characterization of Structure and NMR Spectra.
abstract: The structure and NMR spectroscopic properties of [Y(C(SiH(CH3)2)3)3] are investigated with density functional theory calculations. The existence of a C3 principal axis that was found experimentally is reproduced, but the calculations also find that the symmetry of the equilibrium structure of [Y(C(SiH(CH3)2)3)3] has to be reduced from the experimentally suggested C3v or C3h to C3 in order to explain the observed SiH NMR chemical shifts. We show that the apparent mirror plane relating two agostic SiH(CH3)2 groups on each ligand is caused by the rapid interchange of the position of the third ligand, which could only be observed at much lower temperatures than used previously in the experiments.
authors.affiliation: School of Chemical and Physical Sciences, Victoria University of Wellington, Kelburn Campus, Wellington 6140, New Zealand, Center for Theoretical Chemistry and Physics, New Zealand Institute for Advanced Study, Massey University Auckland, Private Bag 102904, North Shore City, Auckland 0745, New Zealand, and Institute of Natural Sciences, Massey University Auckland, Private Bag 102904, North Shore City, Auckland 0745, New Zealand.
authors.forename: Matthias
authors.initials: M
authors.lastname: Lein
authors.affiliation: School of Chemical and Physical Sciences, Victoria University of Wellington, Kelburn Campus, Wellington 6140, New Zealand, Center for Theoretical Chemistry and Physics, New Zealand Institute for Advanced Study, Massey University Auckland, Private Bag 102904, North Shore City, Auckland 0745, New Zealand, and Institute of Natural Sciences, Massey University Auckland, Private Bag 102904, North Shore City, Auckland 0745, New Zealand.
authors.forename: John A
authors.initials: JA
authors.lastname: Harrison