TY - JOUR
T1 - Synthesis and Characterization of the Isoelectronic d10 Species [Cu{N(SiMePh2)2}2]- and Zn{N(SiMePh2)2}2
AU - Power, Philip P.
AU - Ruhlandt-Senge, Karin
AU - Shoner, Steven C.
PY - 1991/12/1
Y1 - 1991/12/1
N2 - The compounds [Li(THF)4] [Cu{N(SiMePh2)2)2] (1) and Zn{N(SiMePh2)2}2 (2) have been synthesized and characterized by X-ray crystallography and IR and 1H NMR spectroscopy. They were prepared by the reaction of 2 equiv of LiN(SiMePh2)2 with CuBr or ZnCl2 in Et2O or THF solution. The compounds form part of the series M{N(SiMePh2)2}2 (M = Mn (3), Fe (4), Co (5)) which display N-M-N angles in the range 147.0 (1)-170.7 (1)°. In contrast, the N-Cu-N and N-Zn-N moieties have almost perfectly linear angles at the metal of 179.2 (2) and 177.5 (2)°. The average Cu-N and Zn-N distances are near 1.88 and 1.85 Å. The major conclusion from the structural data is that the angle at the metal is not necessarily determined by the metal size and that secondary interactions between low-lying unfilled metal orbitals and the electron-rich phenyl group(s) play a key role in determining the overall structure. Crystal data with Mo Kα radiation (λ = 0.71069 Å) at 130 K: 1, a = 17.643 (4) Å, b = 14.433 (3) Å, c = 26.085 (10) Å, β = 98.79 (2)°, Z = 4, space group P21/c, 6487 (I> 2σ(I)) data, R = 0.072; 2, a = 10.917 (5) Å, b = 15.485 (8) Å, c = 26.963 (14) Å, β = 90.81 (4)°, Z = 4, space group P21/c, 3894 (I > 2σ(I)) data, R = 0.055.
AB - The compounds [Li(THF)4] [Cu{N(SiMePh2)2)2] (1) and Zn{N(SiMePh2)2}2 (2) have been synthesized and characterized by X-ray crystallography and IR and 1H NMR spectroscopy. They were prepared by the reaction of 2 equiv of LiN(SiMePh2)2 with CuBr or ZnCl2 in Et2O or THF solution. The compounds form part of the series M{N(SiMePh2)2}2 (M = Mn (3), Fe (4), Co (5)) which display N-M-N angles in the range 147.0 (1)-170.7 (1)°. In contrast, the N-Cu-N and N-Zn-N moieties have almost perfectly linear angles at the metal of 179.2 (2) and 177.5 (2)°. The average Cu-N and Zn-N distances are near 1.88 and 1.85 Å. The major conclusion from the structural data is that the angle at the metal is not necessarily determined by the metal size and that secondary interactions between low-lying unfilled metal orbitals and the electron-rich phenyl group(s) play a key role in determining the overall structure. Crystal data with Mo Kα radiation (λ = 0.71069 Å) at 130 K: 1, a = 17.643 (4) Å, b = 14.433 (3) Å, c = 26.085 (10) Å, β = 98.79 (2)°, Z = 4, space group P21/c, 6487 (I> 2σ(I)) data, R = 0.072; 2, a = 10.917 (5) Å, b = 15.485 (8) Å, c = 26.963 (14) Å, β = 90.81 (4)°, Z = 4, space group P21/c, 3894 (I > 2σ(I)) data, R = 0.055.
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U2 - 10.1021/ic00026a029
DO - 10.1021/ic00026a029
M3 - Article
AN - SCOPUS:0000612104
SN - 0020-1669
VL - 30
SP - 5013
EP - 5015
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 26
ER -