固态中的阴离子卤化物···醇簇

Anionic halide···alcohol clusters in the solid state.

作者信息

Gushchin Pavel V, Kuznetsov Maxim L, Haukka Matti, Kukushkin Vadim Yu

机构信息

Institute of Chemistry, Saint Petersburg State University , 198504 Stary Petergof, Russian Federation.

出版信息

J Phys Chem A. 2014 Oct 9;118(40):9529-39. doi: 10.1021/jp506256a. Epub 2014 Sep 23.

DOI:10.1021/jp506256a

PMID:25192004

Abstract

The cationic (1,3,5-triazapentadiene)Pt(II) complexes 12, 22, 32, and 42, were crystallized from ROH-containing systems (R = Me, Et) providing alcohol solvates studied by X-ray diffraction. In the crystal structures of [1-4][(Hal)2(ROH)2] (R = Me, Et), the Hal(-) ion interacts with two or three cations 1-4 by means of two or three or four contacts thus uniting stacked arrays of complexes into the layers. The solvated MeOH or EtOH molecules occupy vacant space, giving contacts with 1-4, and connects to the Hal(-) ion through a hydrogen bridge via the H(1O)O(1S) H atom forming, by means of the Hal(-)···HOR (Hal = Cl, Br) contact, the halide-alcohol cluster. Properties of the Cl(-)···HO(Me) H-bond in [1][(Cl)2(MeOH)2] were analyzed using theoretical DFT methods.

摘要

阳离子型(1,3,5 - 三氮杂戊二烯)铂(II)配合物1₂、2₂、3₂和4₂，从含ROH的体系（R = 甲基、乙基）中结晶出来，得到通过X射线衍射研究的醇溶剂化物。在[1 - 4][(Hal)₂(ROH)₂]（R = 甲基、乙基）的晶体结构中，Hal⁻离子通过两个、三个或四个接触与两个或三个阳离子[1 - 4]²⁺相互作用，从而将配合物的堆叠阵列结合成层。溶剂化的甲醇或乙醇分子占据空位，与[1 - 4]²⁺形成接触，并通过H(1O)O(1S) H原子经由氢键与Hal⁻离子相连，借助Hal⁻···HOR（Hal = Cl、Br）接触形成卤化物 - 醇簇。使用理论DFT方法分析了[1][(Cl)₂(MeOH)₂]中Cl⁻···HO(甲基)氢键的性质。