Synthesis and Characterization of (smif) 2M n (n = 0, M = V, Cr, Mn, Fe,Co, Ni, Ru; N = +1, M = Cr, Mn, Co, Rh, Ir; Smif =1,3-di-(2-pyridyl)-2-azaallyl)

Frazier BA, Bartholomew ER, Wolczanski PT, Debeer S, Santiago-Berrios M, Abruna HD, Lobkovsky EB, Bart SC, Mossin S, Meyer K, Cundari TR (2011)

Publication Type: Journal article, Original article

Publication year: 2011

Journal

Inorganic Chemistry American Chemical Society

Original Authors: Frazier B.A., Bartholomew E.R., Wolczanski P.T., DeBeer S., Santiago-Berrios M., Abruna H.D., Lobkovsky E.B., Bart S.C., Mossin S., Meyer K., Cundari T.R.

Publisher: American Chemical Society

Book Volume: 50

Pages Range: 12414-12436

Journal Issue: 24

DOI: 10.1021/ic200376f

Abstract

A series of Werner complexes featuring the tridentate ligand smif, that is, 1,3-di-(2-pyridyl)-2-azaallyl, have been prepared. Syntheses of (smif) M (1-M; M = Cr, Fe) were accomplished via treatment of M(NSiMe ) (THF) (M = Cr, n = 2; Fe, n = 1) with 2 equiv of (smif)H (1,3-di-(2-pyridyl)-2- azapropene); ortho -methylated ( Mesmif) Fe (2-Fe) and ( Me2smif) Fe (3-Fe) were similarly prepared. Metatheses of MX variants with 2 equiv of Li(smif) or Na(smif) generated 1-M (M = Cr, Mn, Fe, Co, Ni, Zn, Ru). Metathesis of VCl3(THF) with 2 Li(smif) with a reducing equiv of Na/Hg present afforded 1-V, while 2 Na(smif) and IrCl (THF) in the presence of NaBPh gave [(smif) Ir]BPh (1+-Ir). Electrochemical experiments led to the oxidation of 1-M (M = Cr, Mn, Co) by AgOTf to produce [(smif)2M]OTf (1+-M), and treatment of Rh (O CCF ) with 4 equiv Na(smif) and 2 AgOTf gave 1+-Rh. Characterizations by NMR, EPR, and UV-vis spectroscopies, SQUID magnetometry, X-ray crystallography, and DFT calculations are presented. Intraligand (IL) transitions derived from promotion of electrons from the unique CNC (nonbonding) orbitals of the smif backbone to ligand π*-type orbitals are intense (σ ≈ 10 000-60 000 M cm ), dominate the UV-visible spectra, and give crystals a metallic-looking appearance. High energy k-edge spectroscopy was used to show that the smif in 1-Cr is redox noninnocent, and its electron configuration is best described as (smif(-))(smif(2-))Cr(III); an unusual S = 1 EPR spectrum (X-band) was obtained for 1-Cr. © 2011 American Chemical Society.

Authors with CRIS profile

Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Cornell University US United States (USA) (US) University of North Texas (UNT) US United States (USA) (US)

How to cite

APA:

Frazier, B.A., Bartholomew, E.R., Wolczanski, P.T., Debeer, S., Santiago-Berrios, M., Abruna, H.D.,... Cundari, T.R. (2011). Synthesis and Characterization of (smif) 2M n (n = 0, M = V, Cr, Mn, Fe,Co, Ni, Ru; N = +1, M = Cr, Mn, Co, Rh, Ir; Smif =1,3-di-(2-pyridyl)-2-azaallyl). Inorganic Chemistry, 50(24), 12414-12436. https://dx.doi.org/10.1021/ic200376f

MLA:

Frazier, Brenda A., et al. "Synthesis and Characterization of (smif) 2M n (n = 0, M = V, Cr, Mn, Fe,Co, Ni, Ru; N = +1, M = Cr, Mn, Co, Rh, Ir; Smif =1,3-di-(2-pyridyl)-2-azaallyl)." Inorganic Chemistry 50.24 (2011): 12414-12436.

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