Amide Complexes of Zirconium, Rhodium, and Iridium: Synthesis and Reactivity. X-ray Crystal Structures of (η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>Zr(NHC<sub>6</sub>H<sub>4</sub>-<i>o</i>-SMe)<sub>2</sub> and [Rh(μ-SC<sub>6</sub>H<sub>4</sub>-<i>o</i>-NHMe)(COD)]<sub>2</sub><sup>†</sup>
journal contribution
posted on 1998-03-15, 00:00 authored by Rosa Fandos, Martín Martínez-Ripoll, Antonio Otero, María José Ruiz, Ana Rodríguez, Pilar TerrerosThe reaction of Cp<sub>2</sub>ZrCl<sub>2</sub> (Cp =
η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>) with 2 equiv of the
lithium amide derivative
LiNHC<sub>6</sub>H<sub>4</sub>-<i>o</i>-SMe affords the new
zirconium complex
Cp<sub>2</sub>Zr(NHC<sub>6</sub>H<sub>4</sub>-<i>o</i>-SMe)<sub>2</sub>
(<b>2</b>). The
structure of <b>2 </b>has been determined by X-ray diffraction.
When the reaction is carried out
in an 1:1 ratio, the complex
Cp<sub>2</sub>ZrCl(NHC<sub>6</sub>H<sub>4</sub>-<i>o</i>-SMe)
(<b>3</b>) is generated as the major product.
Reaction of “Cp*<sub>2</sub>Zr” (Cp* =
η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>) with
2-(methylmercapto)aniline yields a hydride−amide complex
Cp*<sub>2</sub>ZrH(NHC<sub>6</sub>H<sub>4</sub>)
(<b>4</b>). Reaction of complex <b>2</b> with
[RhCl(COD)]<sub>2</sub> generates
complex <b>3</b> and the new rhodium amide complex
Rh(NHC<sub>6</sub>H<sub>4</sub>-<i>o</i>-SMe)(COD),
which has been
also directly synthesized by reacting [RhCl(COD)]<sub>2</sub>
with LiNHC<sub>6</sub>H<sub>4</sub>-<i>o</i>-SMe.
Thermolysis of
complex <b>6</b>, at 100 °C, produces to a new rhodium thiolate
complex
[Rh(μ-SC<sub>6</sub>H<sub>4</sub>-<i>o</i>-NHMe)(COD)]<sub>2</sub> (<b>5</b>). Its structure has been
determined by X-ray diffraction methods. Reaction of
[IrCl(COD)]<sub>2</sub> with
LiNHC<sub>6</sub>H<sub>4</sub>-<i>o</i>-SMe gives the
iridium(III) complex
Ir(Me)(SC<sub>6</sub>H<sub>4</sub>NH)(COD)
(<b>7</b>) by oxidative addition of the S−Me bond.
