钌蓝配合物[Ru(2)Cl(3)(tacn)(2)](PF(6))(2).4H(2)O、[Ru(2)Br(3)(tacn)(2)](PF(6))(2).2H(2)O和[Ru(2)I(3)(tacn)(2)](PF(6))(2)的X射线晶体学研究：空间相互作用与Ru-Ru“键长”

X-ray Crystallographic Study of the Ruthenium Blue Complexes [Ru(2)Cl(3)(tacn)(2)](PF(6))(2).4H(2)O, [Ru(2)Br(3)(tacn)(2)](PF(6))(2).2H(2)O, and [Ru(2)I(3)(tacn)(2)](PF(6))(2): Steric Interactions and the Ru-Ru "Bond Length".

作者信息

Clucas Wendy A., Armstrong Robert S., Buys Irmi E., Hambley Trevor W., Nugent Kerry W.

机构信息

School of Chemistry, University of Sydney, Sydney, NSW 2006, Australia.

出版信息

Inorg Chem. 1996 Nov 6;35(23):6789-6794. doi: 10.1021/ic9605377.

DOI:10.1021/ic9605377

PMID:11666844

Abstract

X-ray crystal structures are reported for the following complexes: Ru(2)Cl(3)(tacn)(2)(2).4H(2)O (tacn = 1,4,7-triazacyclononane), monoclinic P2(1)/n, Z = 4, a = 14.418(8) Å, b = 11.577(3) Å, c = 18.471(1) Å, beta = 91.08(5) degrees, V = 3082 Å(3), R(R(w)) = 0.039 (0.043) using 4067 unique data with I > 2.5sigma(I) at 293 K; Ru(2)Br(3)(tacn)(2)(2).2H(2)O, monoclinic P2(1)/a, Z = 4, a = 13.638(4) Å, b = 12.283(4) Å, c = 18.679(6) Å, beta = 109.19(2) degrees, V = 3069.5 Å(3), R(R(w)) = 0.052 (0.054) using 3668 unique data with I > 2.5sigma(I) at 293 K; Ru(2)I(3)(tacn)(2)(2), cubic P2(1)/3, Z = 3, a = 14.03(4) Å, beta = 90.0 degrees, V = 2763.1(1) Å(3), R (R(w)) = 0.022 (0.025) using 896 unique data with I > 2.5sigma(I) at 293 K. All of the cations have cofacial bioctahedral geometries, although Ru(2)Cl(3)(tacn)(2)(2).4H(2)O, Ru(2)Br(3)(tacn)(2)(2).2H(2)O, and Ru(2)I(3)(tacn)(2)(2) are not isomorphous. Average bond lengths and angles for the cofacial bioctahedral cores, N(3)Ru(&mgr;-X)(3)RuN(3), are compared to those for the analogous ammine complexes Ru(2)Cl(3)(NH(3))(6)(2) and Ru(2)Br(3)(NH(3))(6). The Ru-Ru distances in the tacn complexes are longer than those in the equivalent ammine complexes, probably as a result of steric interactions.

摘要

已报道了以下配合物的X射线晶体结构：Ru₂Cl₃(tacn)₂₂·4H₂O（tacn = 1,4,7 - 三氮杂环壬烷），单斜晶系，P2₁/n，Z = 4，a = 14.418(8) Å，b = 11.577(3) Å，c = 18.471(1) Å，β = 91.08(5)°，V = 3082 Å³，在293 K下使用4067个I > 2.5σ(I)的独立数据时，R(Rw) = 0.039 (0.043)；Ru₂Br₃(tacn)₂₂·2H₂O，单斜晶系，P2₁/a，Z = 4，a = 13.638(4) Å，b = 12.283(4) Å，c = 18.679(6) Å，β = 109.19(2)°，V = 3069.5 Å³，在293 K下使用3668个I > 2.5σ(I)的独立数据时，R(Rw) = 0.052 (0.054)；Ru₂I₃(tacn)₂₂，立方晶系，P2₁/3，Z = 3，a = 14.03(4) Å，β = 90.0°，V = 2763.1(1) Å³，在293 K下使用896个I > 2.5σ(I)的独立数据时，R(Rw) = 0.022 (0.025)。所有阳离子均具有共面双八面体几何结构，尽管Ru₂Cl₃(tacn)₂₂·4H₂O、Ru₂Br₃(tacn)₂₂·2H₂O和Ru₂I₃(tacn)₂₂并非同构。将共面双八面体核[N₃Ru(μ - X)₃RuN₃]²⁺的平均键长和键角与类似的氨配合物Ru₂Cl₃(NH₃)₆₂和Ru₂Br₃(NH₃)₆的进行了比较。tacn配合物中的Ru - Ru距离比相应氨配合物中的长，这可能是空间相互作用的结果。