Snapshots of magnesium-centred diborane heterolysis by an outer sphere SN 2 process

Chemical Science
Anne-Frédérique PécharmanMary F Mahon

Abstract

Reactions of the β-diketiminato magnesium diboranate derivative, [(BDI)Mg{pinB(n-Bu)Bpin}] (BDI = HC{(Me)CNDipp}2; Dipp = 2,6-i-Pr2C6H3), with N,N'-dialkyl and N,N'-diaryl carbodiimides provided the corresponding C-borylated magnesium borylamidinates. This reactivity occurs with the displacement of n-BuBpin and with the apparent addition of a nucleophilic {Bpin} anion to the electrophilic unsaturated carbodiimide carbon centres. In contrast, while analogous reactions of [(BDI)Mg{pinB(n-Bu)Bpin}] with N-alkyl or N-aryl aldimines and ketimines also resulted in facile displacement of n-BuBpin, they provided the organomagnesium products of {Bpin} addition to the imine nitrogen atom rather than the more electrophilic trigonal imine carbon. Computational assessment by density functional theory (DFT) indicated that, although the energetic differences are marginal, the organomagnesium products may be considered as the kinetic outcome of these reactions with respect to the generation of alternative amidomagnesium regioisomers. This latter deduction was borne out by the thermally-induced conversion of two such organomagnesium species to their C-borylated amidomagnesium isomers, both of which occur with negligible entropies of activation ...Continue Reading

References

Oct 7, 2006·Science·Todd B Marder
Feb 21, 2007·Angewandte Chemie·Holger Braunschweig
Jul 17, 2007·Journal of the American Chemical Society·Makoto YamashitaKyoko Nozaki
Jun 21, 2008·Angewandte Chemie·Holger BraunschweigKrzysztof Radacki
Nov 5, 2008·Journal of the American Chemical Society·Yasutomo SegawaKyoko Nozaki
Feb 17, 2010·Angewandte Chemie·Holger BraunschweigThomas Kupfer
Sep 21, 2010·Chemical Communications : Chem Comm·Steven B ThorpeWebster L Santos
Sep 21, 2010·Angewandte Chemie·Julien MonotEmmanuel Lacôte
Dec 2, 2010·Journal of the American Chemical Society·James F DunneAaron D Sadow
Oct 1, 2011·Journal of the American Chemical Society·James F DunneAaron D Sadow
Oct 21, 2011·Angewandte Chemie·Eduard BernhardtNikolai Ignatiev
Feb 18, 2012·Chemical Society Reviews·Jessica CidElena Fernández
Mar 27, 2012·Journal of the American Chemical Society·Andrey V ProtchenkoSimon Aldridge
Nov 30, 2012·Chemical Communications : Chem Comm·Debabrata MukherjeeAaron D Sadow
Jun 15, 2013·Angewandte Chemie·David A RuizGuy Bertrand
Mar 22, 2014·Nature Chemistry·Andrey V ProtchenkoSimon Aldridge
Jun 10, 2014·Chemical Communications : Chem Comm·David A RuizGuy Bertrand
Nov 25, 2014·Chemical Communications : Chem Comm·T ArnoldJ K Schuster
Dec 18, 2014·Chemical Communications : Chem Comm·Nuria MirallesElena Fernández
Feb 24, 2015·Chemical Communications : Chem Comm·Johannes LandmannMaik Finze
Apr 29, 2015·Chemical Communications : Chem Comm·Rian D DewhurstTodd B Marder
Sep 12, 2015·Angewandte Chemie·David J LiptrotAndrew S S Wilson
Jan 16, 2016·Angewandte Chemie·Holger BraunschweigQing Ye
Jan 23, 2016·Chemical Society Reviews·Michael S HillCatherine Weetman
Mar 5, 2016·Angewandte Chemie·Núria MirallesElena Fernández
Apr 14, 2016·Chemistry : a European Journal·Catherine WeetmanMary F Mahon
Jun 10, 2016·Nature Communications·Baolin WangRei Kinjo
Jul 20, 2016·Chemical Reviews·Emily C NeeveTodd B Marder
Dec 13, 2016·Chemical Society Reviews·Ana B CuencaElena Fernández

❮ Previous
Next ❯

Citations

Sep 13, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Daniel VoglerHans-Jörg Himmel
Dec 13, 2019·Angewandte Chemie·Ryan J SchwammAndrew S S Wilson
Feb 15, 2020·Angewandte Chemie·Timo TrageserMatthias Wagner
May 14, 2020·Angewandte Chemie·Anne-Frédérique PécharmanMary F Mahon
Jul 12, 2019·Chemical Communications : Chem Comm·Anne-Frédérique PécharmanMary F Mahon
Apr 22, 2020·Angewandte Chemie·Ryan J SchwammAndrew S S Wilson
Aug 8, 2020·Chemistry : a European Journal·Samantha A OrrVictoria L Blair
Jan 5, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Henry ShereMary F Mahon
Sep 5, 2020·Inorganic Chemistry·Bibian Okokhere-EdeghoghonNasir A Rajabi
Aug 18, 2021·Chemistry : a European Journal·Ryan J SchwammNasir A Rajabi
Nov 16, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Minling ZhongZuowei Xie

❮ Previous
Next ❯

Methods Mentioned

BETA
X-ray
NMR

Related Concepts

Related Feeds

Basal Ganglia

Basal Ganglia are a group of subcortical nuclei in the brain associated with control of voluntary motor movements, procedural and habit learning, emotion, and cognition. Here is the latest research.

Related Papers

Dalton Transactions : an International Journal of Inorganic Chemistry
Anne-Frédérique PécharmanMary F Mahon
Dalton Transactions : an International Journal of Inorganic Chemistry
Andrés G AlgarraStuart A Macgregor
Dalton Transactions : an International Journal of Inorganic Chemistry
Lisa A-M HarrisJ Robin Fulton
Nature Communications
Anne-Frédérique PécharmanCatherine Weetman
© 2021 Meta ULC. All rights reserved