四甲基溴化铵辅助下Se-Br反应：[(CH3)4N]2[Se16Br18]的合成与晶体结构
需积分: 9 115 浏览量
更新于2024-08-07
收藏 154KB PDF 举报
该研究论文详细探讨了在四甲基溴化铵存在下的硒与溴（Se:Br = 1:1）在乙腈溶液中的反应过程，着重于合成了一种新颖的化合物——[(CH3)4N]2[Se16Br18]，这是一种具有独特结构的溴硒酸盐（I）负离子的盐类。该实验由Vitalijus Janickis等人进行，他们分别来自立陶宛、挪威和德国的研究机构。
研究人员在合成过程中，选择乙腈作为溶剂，利用四甲基铵溴化物作为催化剂，使硒和溴发生反应，最终得到红色晶体形式的[(CH3)4N]2[Se16Br18]。这种化合物的晶体结构经过精确测定，结晶在单斜晶系P21/n空间群中，具有特定的单元细胞参数：a = 12.1876(4) Å, b = 18.9670(4) Å, c = 12.2390(4) Å, β = 91.908(2)°（在123K时测量）。在固体状态下，[Se16Br18]2-阴离子是由两个[Br(Se2Br2)4]亚单位构成，这两个亚单位通过一个对称中心相互连接，并通过弱的Se-Br键（分别为3.2588(9) Å 和 3.3887(9) Å）相联。
这一发现不仅提供了关于硒和溴在特定条件下化学反应的新见解，而且揭示了新型卤素硒酸盐的独特晶体结构。这种结构对于理解硒的多面性以及其在无机化学中的潜在应用具有重要意义，可能涉及到催化剂、光电材料或者其它功能性材料的设计。同时，该研究也为后续关于硒的配合物合成和结构研究奠定了基础，促进了相关领域内的理论和实验探索。
Reaction of Selenium with Bromine (Se:Br ⴝ 1:1) in Acetonitrile in the
Presence of Tetramethylammonium Bromide: Synthesis and Crystal Structure of
[(CH
3
)
4
N]
2
[Se
16
Br
18
], the Salt of a Unique Bromoselenate(I) Anion
Vitalijus Janickis*
,a
, Karl Wilhelm Törnroos
b
, Max Herberhold
c
, Jon Songstad
b
, and Wolfgang Milius
c
a
Kaunas, Lithuania, Faculty of Chemical Technology, Kaunas University of Technology
b
Bergen, Norway, Department of Chemistry, University of Bergen
c
Bayreuth, Germany, Laboratory of Inorganic Chemistry, University of Bayreuth
Received April 16th, 2002.
Abstract. Red crystals of [(CH
3
)
4
N]
2
[Se
16
Br
18
](1) were isolated
when selenium and bromine were allowed to react in acetonitrile
solution in the presence of tetramethylammonium bromide. The
salt 1 crystallizes in the monoclinic space group P 2
1
/n with the cell
dimensions a ⫽ 12.1876(4) A
˚
,b⫽ 18.9670(4) A
˚
,c⫽ 12.2390(4)
A
˚
, β ⫽ 91.908(2) ° (123 K). In the solid state structure the
[Se
16
Br
18
]
2⫺
anion consists of two [Br(Se
2
Br
2
)
4
]
⫺
subunits which
are related by an inversion centre and connected by 4 weak Se⫺Br
bonds (3.2588(9) A
˚
and 3.3887(9) A
˚
, respectively). Each
Umsetzung von Selen mit Brom (Se:Br ⴝ 1:1) in Acetonitril in Gegenwart von
Tetramethylammonium-bromid: Synthese und Kristallstruktur von
[(CH
3
)
4
N]
2
[Se
16
Br
18
], dem Salz eines neuartigen Bromoselenat(I)-Anions
Inhaltsübersicht. Rote Kristalle von [(CH
3
)
4
N]
2
[Se
16
Br
18
](1) ließen
sich isolieren, wenn Selen und Brom in Acetonitril-Lösung in Ge-
genwart von Tetramethylammonium-bromid zur Reaktion ge-
bracht wurden. Das Salz 1 kristallisiert in der monoklinen Raum-
gruppe P 2
1
/n mit den Zellkonstanten a ⫽ 12.1876(4) A
˚
,b⫽
18.9670(4) A
˚
,c⫽ 12.2390(4) A
˚
, β ⫽ 91.908(2)° (123 K). In der
Festkörperstruktur besteht das Anion [Se
16
Br
18
]
2⫺
aus zwei
[Br(Se
2
Br
2
)
4
]
⫺
Untereinheiten, die über ein Inversionszentrum in
Zusammenhang stehen und über 4 schwache Se⫺Br Bindungen
Introduction
Selenium and bromine form the binary compounds Se
2
Br
2
,
SeBr
2
and SeBr
4
. In addition, Se
3
Br
2
and Se
4
Br
2
may be
obtained by disproportionation of Se
2
Br
2
. The binary sel-
enium(II) dibromide, SeBr
2
, has not been isolated, although
it is the parent compound of a series of complexes with
bromide ions. Examples of known dianionic bromoselen-
ate(II) complexes (cf. [7]) are the nearly square-planar,
mononuclear [SeBr
4
]
2⫺
ion [1,2], the dinuclear [Se
2
Br
6
]
2⫺
* Prof. Dr. Vitalijus Janickis
Faculty of Chemical Technology
Kaunas University of Technology
Radvile
`
nu
¸
str. 19, LT-3028 Kaunas, Lithuania
FAX: ⫹370 7 451582
E-Mail: vitalijus.janickis@ctf.ktu.lt
Z. Anorg. Allg. Chem. 2002, 628, 1967⫺1974 WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 0044⫺2313/02/628/1967⫺1974 $ 20.00⫹.50/0 1967
monoanionic subunit may be regarded as built up of 4 Se
2
Br
2
mol-
ecules, coordinated to a central bromide ion at distances of
3.0731(9)⫺3.1061(9) A
˚
. The structure of the [Se
16
Br
18
]
2⫺
dianion
can also be formally derived from the known [Se
4
Br
6
]
2⫺
dianion
which uses each of its two bridging bromo ligands for coordination
of 3 additional Se
2
Br
2
molecules.
Keywords: Selenium; Bromoselenates(I); Crystal structure; Tetra-
methylammonium ion
(3.2588(9) bzw. 3.3887(9) A
˚
) miteinander verknüpft sind. Jede der
beiden monoanionischen Untereinheiten lässt sich aus 4 Se
2
Br
2
-
Molekülen aufbauen, die (mit Abständen von 3.0731(9) bis
3.1061(9) A
˚
) an ein zentrales Bromid-Ion koordiniert sind. Die
Struktur des Dianions [Se
16
Br
18
]
2⫺
kann formal auch aus dem be-
kannten Dianion [Se
4
Br
6
]
2⫺
abgeleitet werden, wenn an die beiden
brückenständigen Bromo-Liganden zusätzlich jeweils 3 Moleküle
Se
2
Br
2
angelagert werden.
ion consisting of two edge-sharing distorted SeBr
4
squares
[1,3], the trinuclear [Se
3
Br
8]
2⫺
ion consisting of three edge-
sharing square planar SeBr
4
units [4], the tetranuclear ion
[Se
4
Br
14
]
2⫺
which is formed from two parallel planar Se
2
Br
6
units connected via two linear bromo bridges [4,5] , and the
pentanuclear ion [Se
5
Br
12
]
2⫺
, consisting of a central square
planar SeBr
4
unit with two of its trans-edges being shared
with additional pairs of square planar SeBr
4
units [4].
In contrast to monoselenium dibromide, SeBr
2
, the bi-
nary compound Se
2
Br
2
is stable both as liquid and in the
solid state. It may exist in the modifications α- and β-Se
2
Br
2
which have been characterized by low-temperature crystal
structure analyses [6].
Selenium reacts with bromine in acetonitrile solution,
and when the Se/Br
2
ratio is 2.0, the product is mainly
Se
2
Br
2
:
下载后可阅读完整内容，剩余7页未读，立即下载
2021-06-29 上传
点击了解资源详情
2021-05-14 上传
2021-06-13 上传
2021-05-13 上传
2021-05-30 上传
2021-05-26 上传
2021-05-30 上传
2021-05-13 上传
weixin_38623366
- 粉丝: 4
- 资源: 931
我的内容管理
展开
最新资源
- 黑板风格计算机毕业答辩PPT模板下载
- CodeSandbox实现ListView快速创建指南
- Node.js脚本实现WXR文件到Postgres数据库帖子导入
- 清新简约创意三角毕业论文答辩PPT模板
- DISCORD-JS-CRUD：提升 Discord 机器人开发体验
- Node.js v4.3.2版本Linux ARM64平台运行时环境发布
- SQLight：C++11编写的轻量级MySQL客户端
- 计算机专业毕业论文答辩PPT模板
- Wireshark网络抓包工具的使用与数据包解析
- Wild Match Map: JavaScript中实现通配符映射与事件绑定
- 毕业答辩利器：蝶恋花毕业设计PPT模板
- Node.js深度解析：高性能Web服务器与实时应用构建
- 掌握深度图技术：游戏开发中的绚丽应用案例
- Dart语言的HTTP扩展包功能详解
- MoonMaker: 投资组合加固神器，助力$GME投资者登月
- 计算机毕业设计答辩PPT模板下载
