TY - JOUR
T1 - Synthesis and characterization of low-coordinate divalent aryl transition-metal halide analogues of grignard reagents
T2 - Precursors for reduction to metal-metal-bonded complexes
AU - Sutton, Andrew D.
AU - Ngyuen, Tailuan
AU - Fettinger, James C.
AU - Olmstead, Marilyn M.
AU - Long, Gary J.
AU - Power, Philip P.
PY - 2007/6/11
Y1 - 2007/6/11
N2 - The synthesis and characterization of the series of divalent first-row aryl transition-metal(II) halide compounds [Cr(mu;-Cl)Ar′]2 (1) and (Li(OEt2)Ar′Ml2]2 (M = Mn (2), Fe (3), and Co (4); Ar′ = C6H3-2,6-(C6H 3-2,6-iPr2)2) are described. 1-4 were prepared by the addition of one equiv of Ar′Li to the respective transition-metal dihalides. They were characterized by UV-vis spectroscopy, magnetic measurements, and by X-ray crystallography. In dimeric 1, each chromium center has quasi-four-coordinate, square-planar geometry, in which the metal is terminally bound to a terphenyl ligand through the ipso carbon of the central ring and to two bridging chloride ligands. There is a further interaction between chromium and an ipso carbon from one of the flanking -C 6H3-2,6iPr2 rings. In contrast, for the iodo derivatives 2-4, Lil is not eliminated upon addition of LiAr′ to Ml2. Instead, the diethyl ether solvated adducts, [Li(OEt 2)Ar′MI2]2 (M = Mn (2), Fe (3), or Co (4)) were isolated. These possess a distorted cubane Li2M 2l4 core, in which the lithiums are bound to an ether and the transition metals are bound to a terphenyl group. Magnetic measurements between 2 and 300 K reveal the expected weak antiferromagnetic exchange coupling in each of the complexes.
AB - The synthesis and characterization of the series of divalent first-row aryl transition-metal(II) halide compounds [Cr(mu;-Cl)Ar′]2 (1) and (Li(OEt2)Ar′Ml2]2 (M = Mn (2), Fe (3), and Co (4); Ar′ = C6H3-2,6-(C6H 3-2,6-iPr2)2) are described. 1-4 were prepared by the addition of one equiv of Ar′Li to the respective transition-metal dihalides. They were characterized by UV-vis spectroscopy, magnetic measurements, and by X-ray crystallography. In dimeric 1, each chromium center has quasi-four-coordinate, square-planar geometry, in which the metal is terminally bound to a terphenyl ligand through the ipso carbon of the central ring and to two bridging chloride ligands. There is a further interaction between chromium and an ipso carbon from one of the flanking -C 6H3-2,6iPr2 rings. In contrast, for the iodo derivatives 2-4, Lil is not eliminated upon addition of LiAr′ to Ml2. Instead, the diethyl ether solvated adducts, [Li(OEt 2)Ar′MI2]2 (M = Mn (2), Fe (3), or Co (4)) were isolated. These possess a distorted cubane Li2M 2l4 core, in which the lithiums are bound to an ether and the transition metals are bound to a terphenyl group. Magnetic measurements between 2 and 300 K reveal the expected weak antiferromagnetic exchange coupling in each of the complexes.
UR - http://www.scopus.com/inward/record.url?scp=34347251938&partnerID=8YFLogxK
U2 - 10.1021/ic061121o
DO - 10.1021/ic061121o
M3 - Article
AN - SCOPUS:34347251938
SN - 0020-1669
VL - 46
SP - 4809
EP - 4814
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 12
ER -