Synthesis of a Naphthalene-Bridged Bis(guanidinato)ytterbium(II) Complex and an Unexpected Pathway in Its Reaction with CH<sub>3</sub>CN, <i>p</i>‑ClC<sub>6</sub>H<sub>4</sub>CH<sub>2</sub>CN, and Ph<sub>2</sub>CHCN
dataset
posted on 2016-02-19, 04:08 authored by Chuanyong Wang, Xingmin Zhang, Mingqiang Xue, Yong Zhang, Qi ShenA novel
binuclear ytterbium(II) complex supported by a naphthalene-bridged
bis(guanidinate) ligand, [Yb(μ-L)(THF)]<sub>2</sub> (<b>1</b>; L = 1,8-C<sub>10</sub>H<sub>6</sub>{NC(N<sup><i>i</i></sup>Pr)(NH<sup><i>i</i></sup>Pr)}<sub>2</sub>), was synthesized
by the reduction reaction of [Yb(L)Cl(THF)<sub>2</sub>] with Na/K
alloy in THF and structurally characterized. The reactions of <b>1</b> with CH<sub>3</sub>CN and <i>p</i>-ClC<sub>6</sub>H<sub>4</sub>CH<sub>2</sub>CN resulted in the formation of the corresponding
binuclear (crotononitrileamido)ytterbium(III) complexes [Yb(L)(μ(<i>N,N′</i>)-N(H)C(Me)C(H)CN)(THF)]<sub>2</sub> (<b>2</b>) and [Yb(L)(μ(<i>N</i>,<i>N</i>′)-N(H)C(CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub><i>-p</i>-Cl)C(C<sub>6</sub>H<sub>4</sub><i>-p</i>-Cl)CN)(THF)]<sub>2</sub> (<b>3</b>) via
metalation of the nitrile, followed by insertion of a second nitrile
molecule. Treatment of <b>1</b> with the bulkier Ph<sub>2</sub>CHCN afforded the mononuclear (keteniminato)ytterbium(III) complex
[Yb(L)(NCCPh<sub>2</sub>)(THF)<sub>2</sub>] (<b>4</b>) by deprotonation of Ph<sub>2</sub>CHCN. The molecular structures
of <b>2</b>–<b>4</b> have been determined.
