合成与结构表征：Cu20Se4(μ3-SePh)12(PPh3)6和Ag(SePh)[infin]分子簇
需积分: 5 70 浏览量
更新于2024-08-07
收藏 223KB PDF 举报
本文是一篇发表于2002年的学术论文，标题为"[Cu20Se4(μ3-SePh)12(PPh3)6]和[Ag(SePh)][infin]的合成与结构表征"，由Heather L. Cuthbert、Andrew I. Wallbank、Nicholas J. Taylor和John F. Corrigan四位作者共同完成，他们在伦敦/加拿大不列颠哥伦比亚大学化学系和滑铁卢/加拿大多伦多大学化学系进行研究。这篇论文的主要关注点是通过化学合成手段制备两种新型的含硒有机金属化合物。
首先，研究者们通过现场生成的锂苯基硒硫醇（由PhSe-SiMe3与烷基锂试剂反应并插入硫元素得到）与三苯基膦（PPh3）溶于氯化铜溶液的反应，成功合成了分子簇复合物[Cu20Se4(μ3-SePh)12(PPh3)6]（化合物1）。这个过程展示了如何利用不同的化学反应步骤来设计和构建复杂金属-硒-硫体系。
接着，他们尝试类似的反应条件，但使用银氯（AgCl）作为金属源，得到了一个更为扩展的结构[Ag(SePh)]，其中银(I)原子被μ4-SePh配体包围，形成了一种无限层结构[Ag(SePh)][infin]（化合物2）。这种结构的变化揭示了在不同的金属中心下，相同的基本反应步骤可以导致截然不同的材料性质和组装模式。
这篇论文的重要性在于它不仅提供了新型有机金属硒化合物的合成方法，还通过详细的结构表征，如可能的X射线晶体学数据、光谱分析等，揭示了它们的晶体结构和可能的功能特性。这些发现对于理解金属硒化合物的化学行为、设计新的催化剂和材料具有重要意义，同时也对理论化学家探索金属-硒-硫系统的基础科学问题有所贡献。
这篇论文深入探讨了在无机-有机界限上的创新合成策略，并为理解和操控这类复杂体系提供了实验依据，对于从事金属有机化学、无机化学以及材料科学领域的研究人员具有很高的参考价值。
Synthesis and Structural Characterization of [Cu
20
Se
4
(µ
3
-SePh)
12
(PPh
3
)
6
] and
[Ag(SePh)]
ⴥ
Heather L. Cuthbert
a
, Andrew I. Wallbank
a
, Nicholas J. Taylor
b
, and John F. Corrigan
a,
*
a
London/Canada, Department of Chemistry, The University of Western Ontario
b
Waterloo/Canada, Department of Chemistry, University of Waterloo
Received June 3
rd
, 2002.
Dedicated to Professor Dieter Fenske (“Partner”) on the Occasion of his 60
th
Birthday
Abstract. Reaction of lithium phenylselenothiolate, generated in
situ from the reductive cleavage of PhSe-SiMe
3
with alkyl lithium
reagents and insertion of elemental sulfur, with triphenylphosphine
solubilized CuCl affords the molecular cluster complex [Cu
20
Se
4
-
(µ
3
-SePh)
12
(PPh
3
)
6
](1). The analogous reaction with AgCl yields
the extended structure [Ag(SePh)]
⬁
(2) in which an infinite layer of
Ag
I
atoms is capped on either side by µ
4
-SePh ligands.
Synthese und strukturelle Charakterisierung von [Cu
20
Se
4
(µ
3
-SePh)
12
(PPh
3
)
6
] und
[Ag(SePh)]
ⴥ
Inhaltsübersicht. Die Reaktion von Lithiumphenylselenothiolat, in
situ durch reduktive Spaltung von PhSe⫺SiMe
3
mit Lithiumalkyl-
Reagenzien und Insertion elementarem Schwefel gebildet, mit in
Triphenylphosphan gelöstem CuCl ergibt den molekularen Cluster-
komplex [Cu
20
Se
4
(µ
3
-SePh)
12
(PPh
3
)
6
](1). Die analoge Reaktion mit
AgCl ergibt [Ag(SePh)]
⬁
(2) mit einer unendlichen Schicht von
Introduction
The chemistry of late transition polynuclear metal-selenol-
ate (⫺SeR) complexes has received broad interest [1] and
has been augmented by the interesting photophysical
properties displayed by these clusters [2]. The synthesis of
higher nuclearity metal-selenolate cluster complexes has
been demonstrated using a variety of approaches including
cleavage of the Se⫺H bond via chalcogenolysis [3] (Eq. (1))
and direct insertion of a chalcogen element into metal
M⫺C bonds (Eq. (2)) [4]. The reaction of anionic selenolate
salts (Eq. (3)) also provides a route into M⫺SeR cluster
complexes [5]. Late transition metal(0) complexes have also
been shown to insert directly into diselenide bonds [6].
* Prof. Dr. John F. Corrigan
Department of Chemistry
The University of Western Ontario
London, Ontario
N6A 5B7 CANADA
Fax: (519) 661-3022
e-mail: corrigan@uwo.ca
Z. Anorg. Allg. Chem. 2002, 628, 2483⫺2488 WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 0044⫺2313/02/628/2483⫺2488 $ 20.00⫹.50/0 2483
1: space group P1
¯
, a ⫽ 17.9510(6), b ⫽ 18.1712(7), c ⫽ 31.4311(11)
A
˚
, α ⫽ 78.098(2), β ⫽ 82.905(2), γ ⫽ 70.012(2)°. 2: space group C2/c,
a ⫽ 5.8762(6), b ⫽ 7.2989(7), c ⫽ 29.124(2) A
˚
, β ⫽ 95.790(3)°.
Keywords: Copper; Silver; Selenium; Phenylselenolate; Cluster
compounds
Ag
I
-Atomen, die an jeder Seite durch µ
4
-SePh-Liganden abge-
deckt ist.
1: Raumgruppe P1
¯
, a ⫽ 17,9510(6), b ⫽ 18,1712(7), c ⫽
31,4311(11) A
˚
, α ⫽ 78,098(2), β ⫽ 82,905(2), γ ⫽ 70,012(2)°. 2:
Raumgruppe C2/c, a ⫽ 5,8762(6), b ⫽ 7,2989(7), c ⫽ 29,124(2) A
˚
,
β ⫽ 95,790(3)°.
L
n
M⫺X ⫹ HSeR 씮 L
n
M⫺SeR ⫹ HX (1)
L
n
M⫺R ⫹ Se 씮 L
n
M⫺SeR (2)
L
n
M-X ⫹ M’
⫹
[RSe]
⫺
씮 L
n
M-SeR ⫹ M’
⫹
X
⫺
(3)
L
n
M-X ⫹ Me
3
SiSeR 씮 L
n
M-SeR ⫹ XSiMe
3
(4)
Fenske and co-workers have demonstrated a wealth of
structural chemistry of copper and silver polynuclear selen-
ide and selenolate complexes when phosphine solublized
copper(I) salts are reacted with Se(SiMe
3
)
2
and/or
RSeSiMe
3
, these reactions driven by the formation of the
silane XSiMe
3
and metal-chalcogen bonding interactions
(Eq. (4)) [7]. The propensity of the heavier chalcogens to
adopt bridging versus terminal bonding modes favors the
formation of polynuclear, cluster complexes. Herein we
report on the synthesis of the polynuclear complex
[Cu
20
Se
4
(µ
3
-SePh)
12
(PPh
3
)
6
](1) and the sheet-like arrange-
ment of the homoleptic silver-selenolate [Ag(SePh)]
⬁
(2).
Results and Discussion
The selenium-silicon bond in PhSeSiMe
3
is cleaved with one
equivalent of butyllithium to generate the anion PhSe
⫺
in
下载后可阅读完整内容，剩余5页未读，立即下载
2021-06-29 上传
2008-11-21 上传
2023-09-04 上传
2024-09-12 上传
2024-09-12 上传
2024-09-12 上传
2024-09-12 上传
weixin_38711041
- 粉丝: 6
- 资源: 954
我的内容管理
展开
最新资源
- 最优条件下三次B样条小波边缘检测算子研究
- 深入解析：wav文件格式结构
- JIRA系统配置指南：代理与SSL设置
- 入门必备：电阻电容识别全解析
- U盘制作启动盘：详细教程解决无光驱装系统难题
- Eclipse快捷键大全：提升开发效率的必备秘籍
- C++ Primer Plus中文版：深入学习C++编程必备
- Eclipse常用快捷键汇总与操作指南
- JavaScript作用域解析与面向对象基础
- 软通动力Java笔试题解析
- 自定义标签配置与使用指南
- Android Intent深度解析：组件通信与广播机制
- 增强MyEclipse代码提示功能设置教程
- x86下VMware环境中Openwrt编译与LuCI集成指南
- S3C2440A嵌入式终端电源管理系统设计探讨
- Intel DTCP-IP技术在数字家庭中的内容保护
