Experimental and quantum chemical studies of anionic analogues of N-heterocyclic carbenes

Dalton Transactions : an International Journal of Inorganic Chemistry
Haoyu NiuSimon Aldridge

Abstract

A combination of quantum chemical and synthetic/crystallographic methods have been employed to probe electronic structure in two series of anionic ligands related to the well known N-heterocyclic carbene (NHC) class of donor. Analyses of (i) the respective frontier orbital energies/compositions for the 'free' ligands and the results of ETS-NOCV studies of the bonding in model group 11 complexes; and (ii) the structural metrics for (new) linear gold(i) compounds, have been used to probe the bonding in complexes of NHC ligands which incorporate a backbone-appended weakly-coordinating anion component (WCA-NHCs) and in systems featuring the isoelectronic (formally anionic) diazaborolyl ligand family. Key findings are that WCA-NHC ligands - in which the anionic component is attached to the ligand heterocycle via a methylene (CH2) spacer - offer electronic (and steric) properties which are largely unperturbed from their 'simple' NHC counterparts, while diazaborolyl donors (in which the negative charge is formally located at the boron donor atom) offer significantly stronger σ-donation and a very high trans influence.

References

Sep 15, 1988·Physical Review A: General Physics·A D Becke
Jun 15, 1986·Physical Review. B, Condensed Matter·J P Perdew
Dec 26, 2001·Chemical Reviews·Didier BourissouGuy Bertrand
Feb 19, 2002·Chemical Reviews·Geoffrey J. IrvineL. James Wright
May 22, 2003·Journal of Computational Chemistry·E Van Lenthe, E J Baerends
Jul 23, 2005·Angewandte Chemie·Manuel R FructosPedro J Pérez
Dec 6, 2005·Inorganic Chemistry·Jun ZhuTodd B Marder
Apr 10, 2008·Angewandte Chemie·F Ekkehardt Hahn, Mareike C Jahnke
May 15, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Beatriz CorderoSantiago Alvarez
Aug 6, 2008·Journal of the American Chemical Society·Vincent CésarGuy Lavigne
Nov 5, 2008·Journal of the American Chemical Society·Yasutomo SegawaKyoko Nozaki
Apr 14, 2009·Chemical Reviews·Joseph C Y LinIvan J B Lin
Jul 2, 2009·Chemical Communications : Chem Comm·Li DangTodd B Marder
Jul 2, 2009·Chemistry : a European Journal·Susanne FlüggeAlois Fürstner
Jul 11, 2009·Chemical Reviews·Silvia Díez-GonzálezSteven P Nolan
Apr 15, 2002·Angewandte Chemie·Wolfgang A Herrmann
Jan 29, 2010·Chemical Communications : Chem Comm·Hervé Clavier, Steven P Nolan
Mar 20, 2010·Chemical Reviews·Holger BraunschweigAchim Schneider
May 8, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Slawomir UrbanFrank Glorius
Aug 18, 2010·Angewandte Chemie·Thomas Dröge, Frank Glorius
Sep 8, 2010·Chemistry : a European Journal·Vincent CésarGuy Lavigne
Oct 30, 2010·Accounts of Chemical Research·Steven P Nolan
Feb 26, 2011·Science·Jeremiah J ScepaniakJeremy M Smith
Oct 15, 2011·Chemistry : a European Journal·Nadia VujkovicGuy Lavigne
Feb 18, 2012·Angewandte Chemie·Sabrina KronigMatthias Tamm
Mar 27, 2012·Journal of the American Chemical Society·Andrey V ProtchenkoSimon Aldridge
Jun 19, 2012·Organometallics·David MartinGuy Bertrand
Jul 26, 2013·Journal of the American Chemical Society·Eugene L KolychevMatthias Tamm
Mar 5, 2014·Chemical Communications : Chem Comm·Andrey V ProtchenkoSimon Aldridge
Mar 22, 2014·Nature Chemistry·Andrey V ProtchenkoSimon Aldridge
Jun 27, 2014·Nature·Matthew N HopkinsonFrank Glorius
Jul 19, 2014·Journal of the American Chemical Society·Andrey V ProtchenkoSimon Aldridge
Sep 10, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Nicholas PhillipsSimon Aldridge
Oct 22, 2016·Nature Chemistry·Arnab RitSimon Aldridge
Apr 5, 2017·Angewandte Chemie·Mohand MelaimiGuy Bertrand

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Methods Mentioned

BETA
X-ray
NMR

Software Mentioned

CrysAlisPro
ETS
DENZO
SuperFlip
SHELXT
NOCV
COSMO
Amsterdam Density Functional ( ADF )
SCALEPACK

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