title: Four-coordinate, planar RuII. A triplet state as a response to a 14-valence electron configuration.
abstract: The ligand (tBu2PCH2SiMe2)2N1- (PNP) in [PNP]RuCl leads to an intermediate spin ground state, S = 1, which has been characterized by NMR and X-ray diffraction as having a planar structure. This spin state is attributed in part to N --> Ru pi donation. DFT calculations confirm that the singlet state lies higher in energy and is nonplanar. The molecule is converted to a diamagnetic product by addition of 2 mol of PhCN. The half-filled orbitals of the S = 1 state are suggested to be the reason agostic interactions do not compensate for the 14-valence electron count.
authors.affiliation: Department of Chemistry and Molecular Structure Center, Indiana University, Bloomington, Indiana 47405, USA.
authors.forename: Lori A
authors.initials: LA
authors.lastname: Watson
authors.forename: Oleg V
authors.initials: OV
authors.lastname: Ozerov
authors.forename: Maren
authors.initials: M
authors.lastname: Pink
authors.forename: Kenneth G
authors.initials: KG
authors.lastname: Caulton