TY - JOUR
T1 - Applications of bis(1-R-imidazol-2-yl)disulfides and diselenides as ligands for main-group and transition metals
T2 - κ2-(N,N) coordination, S-S bond cleavage, and S-S/E-E (E = S, Se) bond metathesis reactions
AU - Figueroa, Joshua S.
AU - Yurkerwich, Kevin
AU - Melnick, Jonathan
AU - Buccella, Daniela
AU - Parkin, Gerard
PY - 2007/10/29
Y1 - 2007/10/29
N2 - Bis(1-R-imidazol-2-yl)disulfides, (mimR)2 (R = Ph, But), and diselenides, (seimMes)2, serve as bidentate N,N-donor ligands for main-group and transition metals. For example, [κ2-(mimBut)2]MCl2 (M = Fe, Co, Ni, Zn), [κ2-(mimPh)2]-MCl 2 (M = Co, Zn), [κ2-(mimBut) 2]CuX (X = Cl, I), and [κ2-(seimMes) 2]MCl2 (M = Fe, Co, Ni) are obtained by treatment of (mimBut)2 or (seimMes)2 with the respective metal halide and have been structurally characterized by X-ray diffraction. On the other hand, the zerovalent nickel complex Ni(PMe 3)4 effects cleavage of the disulfide bond of (mim But)2 to give square-planar trans-Ni(PMe3) 2(mimBut)2 in which the (mimBut) ligands coordinate via nitrogen rather than sulfur, a most uncommon coordination mode for this class of ligands. Although [κ2-(mim R)2]MCl2 (M = Fe, Co, Ni, Zn) are not subject to homolytic cleavage of the S-S bond because the tetravalent state is not readily accessible, the observation that [κ2-(mim Ph)2]CoCl2 and [κ2(mim But)2]CoCl2 form an equilibrium mixture with the asymmetric disulfide [κ2-(mimPh)(mim But)]CoCl2 indicates that S-S bond cleavage via another mechanism is possible. Likewise, metathesis between disulfide and diselenide ligands is observed in the formation of [κ2-(mim But)(seimMes)]-CoCl2 upon treatment of [κ2-(mimBut)2]CoCl2 with [κ2-(seimMes)2]CoCl2.
AB - Bis(1-R-imidazol-2-yl)disulfides, (mimR)2 (R = Ph, But), and diselenides, (seimMes)2, serve as bidentate N,N-donor ligands for main-group and transition metals. For example, [κ2-(mimBut)2]MCl2 (M = Fe, Co, Ni, Zn), [κ2-(mimPh)2]-MCl 2 (M = Co, Zn), [κ2-(mimBut) 2]CuX (X = Cl, I), and [κ2-(seimMes) 2]MCl2 (M = Fe, Co, Ni) are obtained by treatment of (mimBut)2 or (seimMes)2 with the respective metal halide and have been structurally characterized by X-ray diffraction. On the other hand, the zerovalent nickel complex Ni(PMe 3)4 effects cleavage of the disulfide bond of (mim But)2 to give square-planar trans-Ni(PMe3) 2(mimBut)2 in which the (mimBut) ligands coordinate via nitrogen rather than sulfur, a most uncommon coordination mode for this class of ligands. Although [κ2-(mim R)2]MCl2 (M = Fe, Co, Ni, Zn) are not subject to homolytic cleavage of the S-S bond because the tetravalent state is not readily accessible, the observation that [κ2-(mim Ph)2]CoCl2 and [κ2(mim But)2]CoCl2 form an equilibrium mixture with the asymmetric disulfide [κ2-(mimPh)(mim But)]CoCl2 indicates that S-S bond cleavage via another mechanism is possible. Likewise, metathesis between disulfide and diselenide ligands is observed in the formation of [κ2-(mim But)(seimMes)]-CoCl2 upon treatment of [κ2-(mimBut)2]CoCl2 with [κ2-(seimMes)2]CoCl2.
UR - http://www.scopus.com/inward/record.url?scp=35848965055&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=35848965055&partnerID=8YFLogxK
U2 - 10.1021/ic701228y
DO - 10.1021/ic701228y
M3 - Article
C2 - 17900186
AN - SCOPUS:35848965055
SN - 0020-1669
VL - 46
SP - 9234
EP - 9244
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 22
ER -