Preparation, characterization, and magnetic behavior of the ln derivatives (ln = nd, la) of a 2,6-diiminepyridine ligand and corresponding dianion.
An unprecedented Nd[2,6-[[2,6-(i-Pr)(2)C(6)H(5)]N=C(CH(3))](2)(C(5)H(3)N)]NdI(2)(THF) (1) complex was prepared by oxidizing metallic Nd with I(2) in THF and in the presence of 2,6-[[2,6-(i-Pr)(2)C(6)H(5)]N=C(CH(3))](2)(C(5)H(3)N). The magnetic behavior at variable T clearly indicated that the complex should be regarded as a trivalent Nd atom antiferromagnetically coupled to a radical anion. By using the doubly deprotonated form of the diimino pyridine ligand [[2,6-[[2,6-(i-Pr)(2)C(6)H(5)]N-C=CH(2)](2)(C(5)H(3)N)](2-) (2) the corresponding trivalent complexes [[2,6-[[2,6-(i-Pr)(2)C(6)H(5)]N-C=CH(2)](2)(C(5)H(3)N)]Ln (THF)](mu-Cl)(2)[Li(THF)(2)].0.5 (hexane) [Ln = Nd (3), La (4)] were obtained and characterized. Reduction of these species afforded electron transfer to the ligand system which gave ligand dimerization via C-C bond formation through one of the two ene-amido functions of each molecule. The resulting dinuclear [[([2,6-(i-Pr)(2)C(6)H(5)]N-C=(CH(2)))(C(5)H(3)N)([2,6-(i-Pr)(2)C(6)H(5)]N=CCH(2))]Ln(THF)(2)(mu-Cl)[Li(THF)(3)])(2).2(THF) [Ln = Nd (5), La (6)] were isolated and characterized.
Sugiyama
Hiroyasu
H
Department of Chemistry, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada.
Korobkov
Ilia
I
Gambarotta
Sandro
S
Möller
Angela
A
Budzelaar
Peter H M
PH
D000838:Anions / Q000737:chemistry*; D007811:Lanthanum / Q000737:chemistry*; D008024:Ligands; D008280:Magnetics; D008956:Models, Chemical; D015394:Molecular Structure; D009354:Neodymium / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D011725:Pyridines / Q000737:chemistry*; D013057:Spectrum Analysis; D013696:Temperature
D000838:Anions; D008024:Ligands; D009942:Organometallic Compounds; D011725:Pyridines; D009354:Neodymium; D007811:Lanthanum