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Four-Coordinate, Planar Ru(II). A Triplet State as a Response to a 14-Valence Electron Configuration

2003; American Chemical Society; Volume: 125; Issue: 28 Linguagem: Inglês

10.1021/ja035166p

1943-2984

L.A. Watson, Oleg V. Ozerov, Maren Pink, Kenneth G. Caulton,

Synthesis and characterization of novel inorganic/organometallic compounds

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.