• 文献检索
  • 文档翻译
  • 深度研究
  • 学术资讯
  • Suppr Zotero 插件Zotero 插件
  • 邀请有礼
  • 套餐&价格
  • 历史记录
应用&插件
Suppr Zotero 插件Zotero 插件浏览器插件Mac 客户端Windows 客户端微信小程序
定价
高级版会员购买积分包购买API积分包
服务
文献检索文档翻译深度研究API 文档MCP 服务
关于我们
关于 Suppr公司介绍联系我们用户协议隐私条款
关注我们

Suppr 超能文献

核心技术专利：CN118964589B侵权必究
粤ICP备2023148730 号-1Suppr @ 2026

文献检索

告别复杂PubMed语法，用中文像聊天一样搜索，搜遍4000万医学文献。AI智能推荐，让科研检索更轻松。

立即免费搜索

文件翻译

保留排版，准确专业，支持PDF/Word/PPT等文件格式，支持 12+语言互译。

免费翻译文档

深度研究

AI帮你快速写综述，25分钟生成高质量综述，智能提取关键信息，辅助科研写作。

立即免费体验

关于全金属双核夹心型配合物 M2(η 4-E 4)2 (M=Al、Ga、In；E=Sb、Bi)的理论研究。

Theoretical studies on all-metal binuclear sandwich-like complexes M2(η 4-E 4) 2 (M=Al, Ga, In; E=Sb, Bi).

机构信息

Institute of Chemical Physics, Beijing Institute of Technology, Beijing, 100081, People's Republic of China.

出版信息

J Mol Model. 2012 Aug;18(8):3577-86. doi: 10.1007/s00894-012-1362-y. Epub 2012 Feb 16.

DOI:10.1007/s00894-012-1362-y
PMID:22350296
Abstract

A series of all-metal binuclear sandwich-like complexes with the formula M(2)(η(4)-E(4))(2) (M=Al, Ga, In; E=Sb, Bi) was studied by density functional theory (DFT). The most stable conformer for each of the M(2)(η(4)-E(4))(2) species is the staggered one with D (4d) symmetry. The centred metal-metal bond in each M(2)(η(4)-E(4))(2) species is a covalent single bond, with the main contributors to these covalent bonds being the a(1) and e orbitals. For all these species, the interactions between the centred metal atoms and the all-metal ligands are covalent; η(4)-Sb (4) (2-) has a stronger ability to stabilize metal-metal bonds than η(4)-Bi (4) (2-). Nucleus-independent chemical shifts (NICS) values and molecular orbital (MO) analysis reveal that the all-metal η(4)-Sb (4) (2-) and η(4)-Bi (4) (2-) ligands in M(2)(η(4)-E(4))(2) possess conflicting aromaticity (σ antiaromaticity and π aromaticity), which differs from the all-metal multiple aromatic unit Al (4) (2-). In addition, all of these M(2)(η(4)-E(4))(2) species are stable according to the dissociation energies of M(2)(η(4)-E(4))(2) → 2 M(η(4)-E(4)) and M(2)(η(4)-E(4))(2) → 2 M + 2E(4), and these stable species can be synthesized by two-step substitution reactions: CpZnZnCp + 2E (4) (2-)  → E(4)ZnZnE(4) + 2Cp(-) and E(4)ZnZnE(4) + 2 M (2) (+)  → E(4)MME(4) + 2Zn(+).

摘要

一系列通式为 M(2)(η(4)-E(4))(2)（M=Al、Ga、In；E=Sb、Bi）的全金属双核夹心型配合物，采用密度泛函理论（DFT）进行了研究。每个 M(2)(η(4)-E(4))(2)物种最稳定的构象是具有 D (4d)对称性的交错构象。每个 M(2)(η(4)-E(4))(2)物种的中心金属-金属键是一个共价单键，这些共价键的主要贡献者是 a(1)和 e 轨道。对于所有这些物种，中心金属原子与全金属配体之间的相互作用是共价的；η(4)-Sb (4) (2-)比 η(4)-Bi (4) (2-)具有更强的稳定金属-金属键的能力。核独立化学位移（NICS）值和分子轨道（MO）分析表明，全金属 η(4)-Sb (4) (2-)和 η(4)-Bi (4) (2-)配体在 M(2)(η(4)-E(4))(2)中具有相互矛盾的芳香性（σ反芳香性和π芳香性），这与全金属多芳香单元 Al (4) (2-)不同。此外，根据 M(2)(η(4)-E(4))(2)→2 M(η(4)-E(4))和 M(2)(η(4)-E(4))(2)→2 M(+) + 2 E(4)的离解能，所有这些 M(2)(η(4)-E(4))(2)物种都是稳定的，这些稳定的物种可以通过两步取代反应合成：CpZnZnCp + 2 E (4) (2-)→E(4)ZnZnE(4) + 2 Cp(-)和E(4)ZnZnE(4) + 2 M (2) (+)→E(4)MME(4) + 2Zn(+)。

相似文献

1
Theoretical studies on all-metal binuclear sandwich-like complexes M2(η 4-E 4) 2 (M=Al, Ga, In; E=Sb, Bi).关于全金属双核夹心型配合物 M2(η 4-E 4)2 (M=Al、Ga、In；E=Sb、Bi)的理论研究。
J Mol Model. 2012 Aug;18(8):3577-86. doi: 10.1007/s00894-012-1362-y. Epub 2012 Feb 16.
2
The first binuclear sandwich-like complexes based on the aromatic tetraatomic species.首例基于芳香四原子物种的双核夹心型配合物。
Dalton Trans. 2011 Jul 14;40(26):6922-8. doi: 10.1039/c1dt10508f. Epub 2011 Jun 2.
3
The all non-metal homodinuclear and heterodinuclear sandwich-like compounds C2(η3-L3)2 and BN(η3-L3)2 (L = BCO, BNN and CBO).所有非金属同双核和异双核夹心型化合物 C2(η3-L3)2 和 BN(η3-L3)2（L = BCO、BNN 和 CBO）。
Dalton Trans. 2012 May 21;41(19):5869-78. doi: 10.1039/c2dt12149b. Epub 2012 Mar 28.
4
DFT Study of the Molecular and Electronic Structure of Metal-Free Tetrabenzoporphyrin and Its Metal Complexes with Zn, Cd, Al, Ga, In.DFT 研究无金属四苯并卟啉及其与 Zn、Cd、Al、Ga、In 的金属配合物的分子和电子结构。
Int J Mol Sci. 2022 Jan 15;23(2):939. doi: 10.3390/ijms23020939.
5
Linear M[triple bond]E-Me versus bent M-E-Me: bonding analysis in heavier metal-ylidyne complexes [(Cp)(CO)2M[triple bond]EMe] and metallo-ylidenes [(Cp)(CO)3M-EMe] (M = Cr, Mo, W; E = Si, Ge, Sn, Pb).直链M≡E-Me与弯曲M-E-Me：重金属叶立德配合物[(Cp)(CO)₂M≡EMe]和金属叶立德[(Cp)(CO)₃M-EMe]（M = Cr、Mo、W；E = Si、Ge、Sn、Pb）中的键合分析
Inorg Chem. 2009 Apr 6;48(7):2748-59. doi: 10.1021/ic801072g.
6
Performance assessment of semiempirical molecular orbital methods in the structural prediction of Sb(III) and Bi(III) complexes.半经验分子轨道方法在 Sb(III)和 Bi(III)配合物结构预测中的性能评估。
J Mol Model. 2013 Oct;19(10):4575-84. doi: 10.1007/s00894-013-1974-x.
7
Structural diversity in supramolecular complexes of MCl(3) (M = As, Sb, Bi) with constrained thio- and seleno-ether ligands.MCl(3)（M = As、Sb、Bi）与受限硫代和硒代醚配体形成的超分子配合物的结构多样性。
Inorg Chem. 2010 Oct 4;49(19):9036-48. doi: 10.1021/ic101296e.
8
Terminal U≡E (E = N, P, As, Sb, and Bi) bonds in uranium complexes: a theoretical perspective.铀配合物中的末端U≡E（E = N、P、As、Sb和Bi）键：理论视角
J Phys Chem A. 2015 Feb 5;119(5):922-30. doi: 10.1021/jp512950j. Epub 2015 Jan 26.
9
Electride Characteristics of Some Binuclear Sandwich Complexes of Alkaline Earth Metals, M(η-L) (M = Be, Mg; L = CH, N, P, As).碱土金属双核夹心配合物M(η-L)（M = Be、Mg；L = CH、N、P、As）的电子化物特性
J Phys Chem A. 2020 Nov 25;124(47):9801-9810. doi: 10.1021/acs.jpca.0c08306. Epub 2020 Nov 15.
10
Theoretical study on structures and aromaticities of P5(-) anion, [Ti (eta(5)-P5)]- and sandwich complex [Ti(eta(5)-P5)2]2-.P5(-) 阴离子、[Ti(η(5)-P5)]- 和夹心配合物 [Ti(η(5)-P5)2]2- 的结构与芳香性的理论研究
J Phys Chem A. 2005 Jun 30;109(25):5645-55. doi: 10.1021/jp044395a.

引用本文的文献

1
Isomerism and Biradical Character of Tetrapnictide Dianions: A Computational Study.四氮族元素二价阴离子的异构现象和双自由基特性：一项计算研究
Eur J Inorg Chem. 2020 Oct 8;2020(37):3580-3586. doi: 10.1002/ejic.202000422. Epub 2020 Sep 14.

本文引用的文献

1
Nucleus-Independent Chemical Shifts:  A Simple and Efficient Aromaticity Probe.核独立化学位移：一种简单高效的芳香性探针。
J Am Chem Soc. 1996 Jul 3;118(26):6317-6318. doi: 10.1021/ja960582d.
2
Zinc-zinc bonded decamethyldizincocene Zn2(η(5)-C5Me5)2 as catalyst for the inter- and intramolecular hydroamination reaction.锌-锌键合十甲基二锌环戊二烯基锌配合物 Zn2(η(5)-C5Me5)2 作为分子间和分子内氢胺化反应的催化剂。
Chem Commun (Camb). 2011 Aug 7;47(29):8280-2. doi: 10.1039/c1cc12461g. Epub 2011 Jun 24.
3
Sandwich-like compounds based on the all-metal aromatic unit Al(4)2- and the main-group metals M (M=Li, Na, K, Be, Mg, Ca).
基于全金属芳香单元Al(4)2-和主族金属M（M = Li、Na、K、Be、Mg、Ca）的三明治状化合物。
Chemistry. 2007;13(9):2546-55. doi: 10.1002/chem.200601223.
4
Sandwich complexes based on the "all-metal" Al4 2- aromatic ring.基于“全金属”Al4 2-芳环的夹心配合物。
Chemistry. 2006 Jun 2;12(17):4495-502. doi: 10.1002/chem.200600106.
5
All-metal aromaticity and antiaromaticity.全金属芳香性和反芳香性。
Chem Rev. 2005 Oct;105(10):3716-57. doi: 10.1021/cr030091t.
6
Theoretical and synthetic studies on [Zn2(eta5-C5Me5)2]: analysis of the Zn-Zn bonding interaction.关于[Zn2(η5-C5Me5)2]的理论与合成研究：锌-锌键相互作用分析
Angew Chem Int Ed Engl. 2005 Feb 11;44(8):1244-7. doi: 10.1002/anie.200462175.
7
Decamethyldizincocene, a stable compound of Zn(I) with a Zn-Zn bond.
Science. 2004 Aug 20;305(5687):1136-8. doi: 10.1126/science.1101356.
8
Metal germylyne complexes [Mtbd1;Ge-R] and metallogermylenes [M-Ge-R]: DFT analysis of the systems [(Cp)(CO)(n)()Mtbd1;GeMe] (M = Cr, Mo, W, Fe(2+), n = 2; M = Fe, n = 1) and [(Cp)(CO)(n)()M-GeMe] (M = Cr, Mo, W, n = 3; M = Fe, n = 2).金属锗炔配合物[Mtbd1;Ge-R]和金属锗烯[M-Ge-R]：[(Cp)(CO)(n)()Mtbd1;GeMe]（M = Cr、Mo、W、Fe(2+)，n = 2；M = Fe，n = 1）和[(Cp)(CO)(n)()M-GeMe]（M = Cr、Mo、W，n = 3；M = Fe，n = 2）体系的密度泛函理论分析
J Am Chem Soc. 2003 Feb 12;125(6):1660-8. doi: 10.1021/ja020974m.
9
Peculiar antiaromatic inorganic molecules of tetrapnictogen in Na+Pn4- (Pn = P, As, Sb) and important consequences for hydrocarbons.Na⁺Pn₄⁻（Pn = P、As、Sb）中四氮族元素的奇特反芳香性无机分子及其对碳氢化合物的重要影响
Inorg Chem. 2002 Nov 18;41(23):6062-70. doi: 10.1021/ic020426+.
10
To what extent can aromaticity be defined uniquely?芳香性在多大程度上可以被唯一地定义？
J Org Chem. 2002 Feb 22;67(4):1333-8. doi: 10.1021/jo016255s.