TY - JOUR
T1 - Isolation of dysprosium and yttrium complexes of a three-electron reduction product in the activation of dinitrogen, the (N2)3- radical
AU - Evans, William J.
AU - Fang, Ming
AU - Zucchi, Gaë L.
AU - Furche, Filipp
AU - Ziller, Joseph W.
AU - Hoekstra, Ryan M.
AU - Zink, Jeffrey I.
PY - 2009/8/12
Y1 - 2009/8/12
N2 - DyI2 reacts with 2 equiv of KOAr (OAr = OC6H 3(CMe3)2-2,6) under nitrogen to form not only the (N2)2- complex, [(ArO)2(THF) 2Dy]2(μ-η2:η2-N 2), 1, but also complexes of similar formula with an added potassium ion, [(ArO)2(THF)Dy]2(μ-η2: η2-N2)[K(THF)6], 2, and [(ArO) 2(THF)Dy]2(μ3-η2: η2:η2-N2)K(THF), 3. The 1.396(7) and 1.402(7) Å N-N bond distances in 2 and 3, respectively, are consistent with an (N2)3- ligand, but the high magnetic moment of 4f9 Dy3+ precluded definitive identification. The Y[N(SiMe3)2]3/K reduction system was used to synthesize yttrium analogues of 2 and 3, {[(Me3Si)2N]2(THF)Y}2(μ- η2:η2-N2)[K(THF)6] and {[(Me3Si)2N]2(THF)Y}2(μ 3-η2:η2:η2-N 2)K, that had similar N-N distances and allowed full characterization. EPR, Raman, and DFT studies are all consistent with the presence of (N2)3- in these complexes. 15N analogues were also prepared to confirm the spectroscopic assignments. The DFT studies suggest that the unpaired electron is localized primarily in a dinitrogen π orbital isolated spatially, energetically, and by symmetry from the metal orbitals.
AB - DyI2 reacts with 2 equiv of KOAr (OAr = OC6H 3(CMe3)2-2,6) under nitrogen to form not only the (N2)2- complex, [(ArO)2(THF) 2Dy]2(μ-η2:η2-N 2), 1, but also complexes of similar formula with an added potassium ion, [(ArO)2(THF)Dy]2(μ-η2: η2-N2)[K(THF)6], 2, and [(ArO) 2(THF)Dy]2(μ3-η2: η2:η2-N2)K(THF), 3. The 1.396(7) and 1.402(7) Å N-N bond distances in 2 and 3, respectively, are consistent with an (N2)3- ligand, but the high magnetic moment of 4f9 Dy3+ precluded definitive identification. The Y[N(SiMe3)2]3/K reduction system was used to synthesize yttrium analogues of 2 and 3, {[(Me3Si)2N]2(THF)Y}2(μ- η2:η2-N2)[K(THF)6] and {[(Me3Si)2N]2(THF)Y}2(μ 3-η2:η2:η2-N 2)K, that had similar N-N distances and allowed full characterization. EPR, Raman, and DFT studies are all consistent with the presence of (N2)3- in these complexes. 15N analogues were also prepared to confirm the spectroscopic assignments. The DFT studies suggest that the unpaired electron is localized primarily in a dinitrogen π orbital isolated spatially, energetically, and by symmetry from the metal orbitals.
U2 - 10.1021/ja9036753
DO - 10.1021/ja9036753
M3 - Article
C2 - 19610635
AN - SCOPUS:68249141229
SN - 0002-7863
VL - 131
SP - 11195
EP - 11202
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 31
ER -