title: Bonding Properties of a Novel Inorganometallic Complex, Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) (iPr-DAB = N,N'-Diisopropyl-1,4-diaza-1,3-butadiene), and its Stable Radical-Anion, Studied by UV-Vis, IR, and EPR Spectroscopy, (Spectro-) Electrochemistry, and Density Functional Calculations.
abstract: Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) was synthesized and characterized by UV-vis, IR, (1)H NMR, (13)C NMR, (119)Sn NMR, and mass (FAB(+)) spectroscopies and by single-crystal X-ray diffraction, which proved the presence of a nearly linear Sn-Ru-Sn unit. Crystals of Ru(SnPh(3))(2)(CO)(2)(iPr-DAB).3.5C(6)H(6) form in the triclinic space group P&onemacr; in a unit cell of dimensions a = 11.662(6) Å, b = 13.902(3) Å, c = 19.643(2) Å, alpha = 71.24(2) degrees, beta = 86.91(4) degrees, gamma = 77.89(3) degrees, and V = 2946(3) Å(3). One-electron reduction of Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) produces the stable radical-anion [Ru(SnPh(3))(2)(CO)(2)(iPr-DAB)](*-) that was characterized by IR, and UV-vis spectroelectrochemistry. Its EPR spectrum shows a signal at g = 1.9960 with well resolved Sn, Ru, and iPr-DAB (H, N) hyperfine couplings. DFT-MO calculations on the model compound Ru(SnH(3))(2)(CO)(2)(H-DAB) reveal that the HOMO is mainly of sigma(Sn-Ru-Sn) character mixed strongly with the lowest pi orbital of the H-DAB ligand. The LUMO (SOMO in the reduced complex) should be viewed as predominantly pi(H-DAB) with an admixture of the sigma(Sn-Ru-Sn) orbital. Accordingly, the lowest-energy absorption band of the neutral species will mainly belong to the sigma(Sn-Ru-Sn)-->pi(iPr-DAB) charge transfer transition. The intrinsic strength of the Ru-Sn bond and the delocalized character of the three-center four-electron Sn-Ru-Sn sigma-bond account for the inherent stability of the radical anion.
authors.affiliation: Anorganisch Chemisch Laboratorium, J. H. van 't Hoff Research Institute, Universiteit van Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, The Netherlands, Amsterdam Institute for Molecular Studies, Universiteit van Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, The Netherlands, Afdeling Theoretische Chemie, Vrije Universiteit, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands, J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejskova 3, 182 23 Prague, Czech Republic.
authors.forename: Maxim P.
authors.initials: MP
authors.lastname: Aarnts
authors.forename: Maikel P.
authors.initials: MP
authors.lastname: Wilms
authors.forename: Karin
authors.initials: K
authors.lastname: Peelen
authors.forename: Jan
authors.initials: J
authors.lastname: Fraanje
authors.forename: Kees
authors.initials: K
authors.lastname: Goubitz
authors.forename: Frantisek
authors.initials: F
authors.lastname: Hartl
authors.forename: Derk J.
authors.initials: DJ
authors.lastname: Stufkens
authors.forename: Evert Jan
authors.initials: EJ
authors.lastname: Baerends
authors.forename: Antonín
authors.initials: A
authors.lastname: Vlcek