title: Reduced N-alkyl substituted bis(imino)pyridine cobalt complexes: molecular and electronic structures for compounds varying by three oxidation states.
abstract: The stepwise 1-3 electron reduction of the N-alkyl substituted bis(imino)pyridine cobalt dichloride complexes, ((R)APDI)CoCl(2), was studied where (R)APDI = 2,6-(RN=CMe)(2)C(5)H(3)N, R = C(6)H(11) (Cy), CHMe(2) ((i)Pr). One electron reduction with either zinc metal or NaBEt(3)H furnished the bis(imino)pyridine cobalt monochloride compounds, ((R)APDI)CoCl. X-ray diffraction on the ((iPr)APDI)CoCl derivative established a distortion from square planar geometry where the chloride ligand is lifted out of the idealized cobalt-chelate plane. Superconducting Quantum Interference Device (SQUID) magnetometry on both compounds established spin crossover behavior with an S = 1 state being predominant at room temperature. Computational studies, in combination with experimental results, establish that the triplet spin isomer arises from a high spin Co(II) center (S(Co) = 3/2) antiferromagnetically coupled to a bis(imino)pyridine chelate radical anion, [PDI](-) (S(PDI) = 1/2). At lower temperatures, the Co(II) ion undergoes a spin transition to the low spin form (S(Co) = 1/2) and antiferromagnetic coupling gives rise to the observed diamagnetic ground state. Replacing the chloride ligand with a methyl group, namely ((R)APDI)CoCH(3), also yielded distorted compounds, albeit less pronounced, that are diamagnetic at room temperature. Two electron reduction of the ((R)APDI)CoCl(2) derivatives with excess 0.5% sodium amalgam or 2 equiv of NaBEt(3)H furnished the bis(chelate)cobalt complexes, ((R)APDI)(2)Co, while three electron reduction with 3 equiv of sodium naphthalenide yielded the cobalt dinitrogen anions, [Na(solv)(3)][((R)APDI)CoN(2)] (solv = THF, Et(2)O). Both bis(chelate) compounds were crystallographically characterized and determined to have S = 3/2 ground states by SQUID magnetometry and electron paramagnetic resonance (EPR) spectroscopy. Computational studies, in combination with metrical parameters determined from X-ray diffraction, establish a high spin (S(Co) = 3/2) cobalt(II) center with two bis(imino)pyridine chelate radical anions. Antiferromagnetic coupling between the two chelate centered radicals is mediated by a doubly occupied t(2g) cobalt orbital and gives rise to the observed overall quartet ground state.
authors.affiliation: Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, USA.
authors.forename: Amanda C
authors.initials: AC
authors.lastname: Bowman
authors.forename: Carsten
authors.initials: C
authors.lastname: Milsmann
authors.forename: Eckhard
authors.initials: E
authors.lastname: Bill
authors.forename: Emil
authors.initials: E
authors.lastname: Lobkovsky
authors.forename: Thomas
authors.initials: T
authors.lastname: Weyhermüller
authors.forename: Karl
authors.initials: K
authors.lastname: Wieghardt
authors.forename: Paul J
authors.initials: PJ
authors.lastname: Chirik
mesh_terms: D003035:Cobalt / Q000737:chemistry*; D007097:Imines / Q000138:chemical synthesis* / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008280:Magnetics; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction; D011725:Pyridines / Q000138:chemical synthesis* / Q000737:chemistry; D011789:Quantum Theory; D014961:X-Ray Diffraction
chemical_list: D007097:Imines; D009942:Organometallic Compounds; D011725:Pyridines; D003035:Cobalt