Flexible coordination of bulky amidinates and guanidinates towards rhodium(I): conversion of kinetic to thermodymanic isomers

Dalton Transactions : an International Journal of Inorganic Chemistry
Cameron JonesAndreas Stasch

Abstract

Reactions of the bulky amidinate and guanidinate salts K[(ArN)(2)CR] (R = Bu(t), NPr(i)(2) or N(C(6)H(11))(2); Ar = 2,6-diisopropylphenyl) with [{RhCl(eta(4)-COD)}(2)] (COD = 1,5-cyclooctadiene) lead to KCl elimination and the formation of the complexes, [Rh{(eta(5)-ArN)(ArN)CR}(COD)], in which the anionic ligand coordinates the rhodium centre in an unprecedented eta(5)-cyclohexadienyl mode. The thermal conversions of these complexes to their N,N'-chelated isomers, [Rh{kappa(2)-N,N'-(ArN)(2)CR}(COD)], were carried out and the kinetics of these processes have been shown to be first order. The rates of the isomerisations are inversely proportional to the size of the amidinate or guanidinate backbone substituent. Analogies between the ligating properties of the bulky amidinates and guanidinates used in the study, and those of beta-diketiminates are discussed.

References

Sep 12, 2002·Chemical Reviews·Laurence Bourget-MerleJohn R Severn
Jul 19, 2005·Dalton Transactions : an International Journal of Inorganic Chemistry·Cameron JonesAndreas Stasch
Feb 14, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Martyn P Coles
Feb 16, 2006·Journal of the American Chemical Society·Cameron JonesAndreas Stasch
Mar 15, 2006·Chemistry : a European Journal·Marta MartínLuis A Oro
Sep 28, 2006·Chemical Communications : Chem Comm·Shaun P GreenAndreas Stasch
Jan 3, 2007·Inorganic Chemistry·Shaun P GreenAndreas Stasch
Nov 10, 2007·Science·Shaun P GreenAndreas Stasch

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Citations

Apr 21, 2017·Chemical Society Reviews·Marcus W DroverLaurel L Schafer
Dec 18, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Lea Fohlmeister, Cameron Jones
Aug 18, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Cameron JonesAndreas Stasch
May 24, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Javier Francos, Victorio Cadierno
Apr 15, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Matthew R GytonAlasdair I McKay
Jan 19, 2011·Chemistry : a European Journal·Cameron JonesChristopher J Cramer
Mar 11, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Andreas Stasch, Cameron Jones

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