Butadienyl Diiron Complexes: Nonplanar Metalla-Aromatics Involving σ-Type Orbital Overlap

Angewandte Chemie
Chao YuZhenfeng Xi

Abstract

A new class of nonplanar metalla-aromatics, diiron complexes bridged by a 1,3-butadienyl dianionic ligand, were synthesized in high yields from dilithio reagents and two equivalents of FeBr2 . The complexes consist of two antiferromagnetically coupled high-spin FeII centers, as revealed by magnetometry, Mössbauer spectroscopy, and DFT calculations. Furthermore, experimental (X-ray structural analysis) and theoretical analyses (NICS, ICSS, AICD, MOs) suggest that the complexes are aromatic. Remarkably, this nonplanar metalla-aromaticity is achieved by an uncommon σ-type overlap between the ligand p and metal d orbitals, in sharp contrast to the intensively studied planar aromatic systems featuring delocalized π-type bonding. Specifically, the σ-type interaction between the two Fe 3dxz orbitals and the butadienyl π orbital results in the formation of a six-electron conjugated system and hence enables the aromatic character.

References

Nov 17, 2001·Chemical Reviews·J R Bleeke
Nov 17, 2001·Chemical Reviews·F De Proft, P Geerlings
Jul 19, 2002·Chemical Communications : Chem Comm·Christophe DelasFumie Sato
Jul 21, 2004·Accounts of Chemical Research·Guochen Jia
Oct 13, 2005·Chemical Reviews·Alexander I Boldyrev, Lai-Sheng Wang
Feb 24, 2006·Organic Letters·Hossein Fallah-Bagher-ShaidaeiPaul v R Schleyer
Apr 6, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·L James Wright
May 25, 2006·Angewandte Chemie·Christopher W Landorf, Michael M Haley
Oct 19, 2006·Journal of the American Chemical Society·Wai Yiu HungGuochen Jia
Mar 14, 2007·Current Opinion in Chemical Biology·Barbara KirchnerFrank Neese
Jan 24, 2008·Physical Chemistry Chemical Physics : PCCP·Dmitry Yu ZubarevAlexander I Boldyrev
Nov 14, 2008·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Ling LinMinh Tho Nguyen
Apr 17, 2010·Science·Masaichi SaitoMasahiko Hada
Sep 9, 2010·Journal of the American Chemical Society·George R ClarkL James Wright
Oct 15, 2011·Journal of the American Chemical Society·Wai Yiu HungGuochen Jia
Dec 14, 2011·Journal of Computational Chemistry·Tian Lu, Feiwu Chen
Dec 25, 2012·Inorganic Chemistry·Subramaniam KuppuswamyChristine M Thomas
Aug 10, 2013·Angewandte Chemie·Tomohiro AgouNorihiro Tokitoh
Aug 13, 2013·Angewandte Chemie·Ángela VivancosEleuterio Álvarez
Nov 15, 2013·Accounts of Chemical Research·Xiao-Yu CaoHaiping Xia
Oct 23, 2014·Inorganic Chemistry·You-Yun ZhouChristopher Uyeda
Feb 19, 2015·Chemical Society Reviews·Israel FernándezGabriel Merino
Oct 21, 2016·Angewandte Chemie·Benjamin J Frogley, L James Wright
Dec 20, 2016·Nature·Martin D PeeksHarry L Anderson
Dec 21, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Michael J BehlenChristopher Uyeda
Jan 26, 2017·Chemical Society Reviews·Wangyang MaZhenfeng Xi
Apr 1, 2017·Journal of the American Chemical Society·Yongliang ZhangZhenfeng Xi
Apr 11, 2017·Frontiers in Chemistry·Miquel Solà
May 31, 2017·Journal of the American Chemical Society·Claudia KupperFranc Meyer
Jul 3, 1996·Journal of the American Chemical Society·Paul von Ragué SchleyerNicolaas J R van Eikema Hommes
Dec 2, 2017·Chemistry : a European Journal·Benjamin J Frogley, L James Wright
Dec 21, 2017·Accounts of Chemical Research·Masaichi Saito
Apr 10, 2018·Inorganic Chemistry·Daniel L J BroerePatrick L Holland
Apr 21, 2018·Chemical Science·Junnian WeiZhenfeng Xi
Jun 22, 2018·Accounts of Chemical Research·Congqing Zhu, Haiping Xia
Jul 4, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Fraser S PickMichael D Fryzuk
Jul 10, 2018·Journal of the American Chemical Society·Bhaskar MondalShengfa Ye
Mar 28, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Joachim LoupLutz Ackermann
May 15, 2019·Accounts of Chemical Research·Wei ChenJeffrey I Zink

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Citations

Apr 15, 2021·Accounts of Chemical Research·Yongliang ZhangZhenfeng Xi
Aug 5, 2021·Chemical Communications : Chem Comm·Jinhua LiHaiping Xia
Sep 18, 2021·Journal of the American Chemical Society·Chun TangHaiping Xia

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