Recently  linear Cu(I) complexes of the form [Cu(OR)2]1- have been prepared with three different alkoxide ligands: perfluoro-t-butoxide (OC4F9), hexafluoro-t-butoxide (OC(CH3)(CF3)2), and the hexafluoro-alpha-cumyl alkoxide (OC(Ph)(CF3)2).  The latter derivative has been crystallographically characterized in a trimeric form {(18-C-6)K}[K2{Cu(OR)2}3] in which two K cations bring the three linear [Cu(OR)2]- groups together.  This form requires careful control of the 18-crown-6 stoichiometry, such that the ratio of 18C6 to Cu is 1:3.  Preparation of the Cu(II) alpha-cumyl derivative [Cu(OR)3]1- has been very challenging, and has not been successful to date.  Rather, attempts beginning with Cu(II) have yielded some of the previously-mentioned Cu(I) species and a new square-planar [Cu{?2-OC(CF3)2C6H4O}]- anion with two cumyl alkoxide ligands that have been ortho-C activated to give a Cu(III) center with {O2C2} coordination.  Formation of this interesting organometallic compound will be discussed including X-ray diffraction and solution heteronuclear NMR studies, as well as the EPR spectra of related Cu(II) species.

Hexafluoro-alpha-cumyl alkoxide: Trinuclear activation of O<sub>2</sub> and Cu(III) organometallics

244th National Meeting (2012)

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Hexafluoro-alpha-cumyl alkoxide: Trinuclear activation of O2 and Cu(III) organometallics

Hexafluoro-alpha-cumyl alkoxide: Trinuclear activation of O₂ and Cu(III) organometallics