Transition-metal imido-boroxide complexes: a structural and spectroscopic investigation of the influence of boron

Sarah C. Cole, M. Coles, P. Hitchcock
{"title":"Transition-metal imido-boroxide complexes: a structural and spectroscopic investigation of the influence of boron","authors":"Sarah C. Cole, M. Coles, P. Hitchcock","doi":"10.1039/B207277G","DOIUrl":null,"url":null,"abstract":"The four coordinate compounds Mo(NR)2[OB(mes)2]2 (1, R = tBu; 2, R = Ar = 2,6-iPr2C6H3) have been obtained from the reaction of [(mes)2BOLi(Et2O)n]x with the corresponding Mo(NR)2Cl2(dme) starting material; for structural comparison, Mo(NtBu)2[OCH(mes)2]2 (3) was also synthesised. The related five-coordinate complexes Ti(NtBu)[OB(mes)2]2(py)2 (4) and Ti(NtBu)[OCH(mes)2]2(py)2 (5) were made using analogous procedures. X-Ray structural investigations of 1–5 were performed to assess the effect that the boron atom has on the metal–oxygen and metal–nitrogen(imido) bond lengths and angles. On average, both classes of compound displayed longer metal–oxygen bonds and shorter metal–nitrogen(imido) bonds for the boroxide derivatives. Spectroscopic investigation of the Δδ values for the tert-butylimido derivatives revealed that complexes incorporating the [OB(mes)2]− anion exhibit a reduction in the electron density at the imido nitrogen atom, in agreement with the observations from the solid state structures.","PeriodicalId":17317,"journal":{"name":"Journal of The Chemical Society-dalton Transactions","volume":"5 1","pages":"4168-4174"},"PeriodicalIF":0.0000,"publicationDate":"2002-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"13","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of The Chemical Society-dalton Transactions","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1039/B207277G","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 13

Abstract

The four coordinate compounds Mo(NR)2[OB(mes)2]2 (1, R = tBu; 2, R = Ar = 2,6-iPr2C6H3) have been obtained from the reaction of [(mes)2BOLi(Et2O)n]x with the corresponding Mo(NR)2Cl2(dme) starting material; for structural comparison, Mo(NtBu)2[OCH(mes)2]2 (3) was also synthesised. The related five-coordinate complexes Ti(NtBu)[OB(mes)2]2(py)2 (4) and Ti(NtBu)[OCH(mes)2]2(py)2 (5) were made using analogous procedures. X-Ray structural investigations of 1–5 were performed to assess the effect that the boron atom has on the metal–oxygen and metal–nitrogen(imido) bond lengths and angles. On average, both classes of compound displayed longer metal–oxygen bonds and shorter metal–nitrogen(imido) bonds for the boroxide derivatives. Spectroscopic investigation of the Δδ values for the tert-butylimido derivatives revealed that complexes incorporating the [OB(mes)2]− anion exhibit a reduction in the electron density at the imido nitrogen atom, in agreement with the observations from the solid state structures.
过渡金属亚胺-硼氧化物配合物:硼影响的结构和光谱研究
四个配位化合物Mo(NR)2[OB(mes)2]2 (1, R = tBu;2、R = Ar = 2,6- ipr2c6h3)由[(mes)2BOLi(Et2O)n]x与相应的Mo(NR)2Cl2(dme)原料反应得到;为了进行结构比较,还合成了Mo(NtBu)2[OCH(mes)2]2(3)。用类似的方法制备了相关的五坐标配合物Ti(NtBu)[OB(mes)2]2(py)2(4)和Ti(NtBu)[OCH(mes)2]2(py)2(5)。对1-5的x射线结构进行了研究,以评估硼原子对金属-氧和金属-氮(亚胺)键的长度和角度的影响。平均而言,这两类化合物的硼氧化物衍生物显示较长的金属-氧键和较短的金属-氮(亚胺)键。对叔丁基氨基甲酸酯衍生物Δδ值的光谱研究表明,含有[OB(mes)2]−阴离子的配合物在亚胺氮原子处表现出电子密度的降低,与固体结构的观察结果一致。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 求助全文
来源期刊
自引率
0.00%
发文量
0
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信