Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
X-Ray Structural Elucidation of a Novel Steric Effect of o-Methoxyl Substituents in 2,6-Dimethoxyphenylnickel(II) Complexes Mediated by m-Bromo Substitution
Duanjun XuYasushi KaiKunio MikiNobutami KasaiKoichi NishiwakiMasanori Wada
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1984 Volume 57 Issue 6 Pages 1459-1468

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Abstract

Molecular structures of novel trans-[NiR2L2] complexes, trans-[Ni{C6H3(OMe)2-2,6}2(PR3)2] [PR3=PMe3 (1a), PMe2Ph (1b)], and their m-brominated derivatives, trans-[Ni{C6H(OMe)2-2,6-Br2-3,5}2(PR3)2] [PR3=PMe3 (2a), PMe2Ph (2b)], were determined by X-ray crystal structure analysis. A remarkable effect of m-substitution on the conformation of the o-methoxyl groups was found. This correlated well with the reactivity difference toward carbon monoxide. Crystal data: 1a: monoclinic, space group P21/c, a=8.737(2), b=18.282(3), c=16.319(4) Å, β=105.06(2)°, Z=4, R=0.062; 1b: triclinic, space group P\bar1, a=16.993(5), b=10.180(3), c=17.177(5) Å, α=112.44(2), β=117.59(2), γ=66.25(2)°, Z=3, R=0.060; 2a: monoclinic, space group P21/c, a=9.294(2), b=14.091(3), c=10.770(2) Å, β=92.06(3)°, Z=2, R=0.067; 2b: triclinic, space group P\bar1, a=9.370(1), b=11.387(2), c=9.013(1) Å, α=94.52(2), β=107.24(2), γ=77.35(2)°, Z=1, R=0.058.

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