Completing the Series of +2 Ions for the Lanthanide Elements: Synthesis of Molecular Complexes of Pr2+, Gd2+, Tb2+, and Lu2+

化学 镧系元素 地穴 结晶学 分子 离子 配体(生物化学) 立体化学 有机化学 生物化学 受体
作者
Matthew R. MacDonald,Jefferson E. Bates,Joseph W. Ziller,Filipp Furche,William J. Evans
出处
期刊:Journal of the American Chemical Society [American Chemical Society]
卷期号:135 (26): 9857-9868 被引量:316
标识
DOI:10.1021/ja403753j
摘要

The first examples of crystallographically characterizable complexes of Tb2+, Pr2+, Gd2+, and Lu2+ have been isolated, which demonstrate that Ln2+ ions are accessible in soluble molecules for all of the lanthanides except radioactive promethium. The first molecular Tb2+ complexes have been obtained from the reaction of Cp′3Ln (Cp′ = C5H4SiMe3, Ln = rare earth) with potassium in the presence of 18-crown-6 in Et2O at −35 °C under argon: [(18-crown-6)K][Cp′3Tb], {[(18-crown-6)K][Cp′3Tb]}n, and {[K(18-crown-6)]2(μ-Cp′)}{Cp′3Tb}. The first complex is analogous to previously isolated Y2+, Ho2+, and Er2+ complexes, the second complex shows an isomeric structural form of these Ln2+ complexes, and the third complex shows that [(18-crown-6)K]1+ alone is not the only cation that will stabilize these reactive Ln2+ species, a result that led to further exploration of cation variants. With 2.2.2-cryptand in place of 18-crown-6 in the Cp′3Ln/K reaction, a more stable complex of Tb2+ was produced as well as more stable Y2+, Ho2+, and Er2+ analogs: [K(2.2.2-cryptand)][Cp′3Ln]. Exploration of this 2.2.2-cryptand-based reaction with the remaining lanthanides for which Ln2+ had not been observed in molecular species provided crystalline Pr2+, Gd2+, and Lu2+ complexes. These Ln2+ complexes, [K(2.2.2-cryptand)][Cp′3Ln] (Ln = Y, Pr, Gd, Tb, Ho, Er, Lu), all have similar UV–vis spectra and exhibit Ln–C(Cp′) bond distances that are ∼0.03 Å longer than those in the Ln3+ precursors, Cp′3Ln. These data, as well as density functional theory calculations and EPR spectra, suggest that a 4fn5d1 description of the electron configuration in these Ln2+ ions is more appropriate than 4fn+1.
最长约 10秒,即可获得该文献文件

科研通智能强力驱动
Strongly Powered by AbleSci AI
更新
PDF的下载单位、IP信息已删除 (2025-6-4)

科研通是完全免费的文献互助平台,具备全网最快的应助速度,最高的求助完成率。 对每一个文献求助,科研通都将尽心尽力,给求助人一个满意的交代。
实时播报
刚刚
李爱国应助研友_8Y26PL采纳,获得10
1秒前
2秒前
阿冬呐完成签到,获得积分10
3秒前
哈哈伊发布了新的文献求助10
3秒前
4秒前
dd发布了新的文献求助80
4秒前
mouxq发布了新的文献求助10
5秒前
归尘应助大吉岭采纳,获得10
6秒前
海东来给凩飒的求助进行了留言
6秒前
蜡笔完成签到,获得积分10
6秒前
九姑娘完成签到 ,获得积分10
7秒前
vvvaee发布了新的文献求助10
7秒前
量子星尘发布了新的文献求助10
9秒前
lsy完成签到,获得积分10
10秒前
Sensons完成签到,获得积分10
10秒前
嘟嘟发布了新的文献求助10
11秒前
12秒前
金旭完成签到,获得积分10
13秒前
RG完成签到,获得积分10
13秒前
13秒前
14秒前
FLZLC发布了新的文献求助10
15秒前
长白完成签到,获得积分10
15秒前
15秒前
15秒前
诸天蓉发布了新的文献求助10
15秒前
敏哇哇哇发布了新的文献求助10
16秒前
17秒前
许雨青发布了新的文献求助30
17秒前
09chenyun完成签到,获得积分10
18秒前
暖暖完成签到,获得积分10
19秒前
刘尹发布了新的文献求助30
19秒前
19秒前
tuanheqi应助松鼠15111采纳,获得100
20秒前
pl脆脆发布了新的文献求助10
20秒前
21秒前
汤圆完成签到,获得积分10
23秒前
23秒前
领导范儿应助明亮依琴采纳,获得10
24秒前
高分求助中
A new approach to the extrapolation of accelerated life test data 1000
Cognitive Neuroscience: The Biology of the Mind 1000
Technical Brochure TB 814: LPIT applications in HV gas insulated switchgear 1000
Toward a Combinatorial Approach for the Prediction of IgG Half-Life and Clearance 500
ACSM’s Guidelines for Exercise Testing and Prescription, 12th edition 500
Picture Books with Same-sex Parented Families: Unintentional Censorship 500
Nucleophilic substitution in azasydnone-modified dinitroanisoles 500
热门求助领域 (近24小时)
化学 材料科学 医学 生物 工程类 有机化学 生物化学 物理 内科学 纳米技术 计算机科学 化学工程 复合材料 遗传学 基因 物理化学 催化作用 冶金 细胞生物学 免疫学
热门帖子
关注 科研通微信公众号,转发送积分 3970008
求助须知:如何正确求助?哪些是违规求助? 3514711
关于积分的说明 11175563
捐赠科研通 3250077
什么是DOI,文献DOI怎么找? 1795198
邀请新用户注册赠送积分活动 875630
科研通“疑难数据库(出版商)”最低求助积分说明 804931