| Summary: | In a refluxing chloroform solution<b>, </b>the η<sup>1</sup>-pyrimidinyl {pyrimidinyl = C<sub>4</sub>H<sub>3</sub>N<sub>2</sub>} palladium complex [Pd(PPh<sub>3</sub>)<sub>2</sub>(η<sup>1</sup>-C<sub>4</sub>H<sub>3</sub>N<sub>2</sub>)(Br)], <b>1</b> exhibited intermolecular displacement of two triphenylphosphine ligands to form the doubly bridged η<sup>2</sup>-pyrimidinyl Dipalladium complex [Pd(PPh<sub>3</sub>)(Br)]<sub>2</sub>(μ,η<sup>2</sup>-C<sub>4</sub>H<sub>3</sub>N<sub>2</sub>)<sub>2</sub>, <b>3</b>. The treatment of <b>1 </b>with Hdppa {Hdppa = <i>N</i>,<i>N</i>-bisdiphenyl phosphinoamine} in refluxing dichloromethane yielded the doubly bridged Hdppa dipalladium complex [Pd(Br)]<sub>2</sub>(μ,η<sup>2</sup>-Hdppa)<sub>2</sub>, <b>4</b>. Complex <b>1</b> reacted with the bidentate ligand, NH<sub>4</sub>S<sub>2</sub>CNC<sub>4</sub>H<sub>8</sub> and, NaS<sub>2</sub>COEt, and the tridentate ligand, KTp {Tp = tris(pyrazoyl-1-yl)borate}, to form the η<sup>2</sup>-dithio η<sup>1</sup>-pyrimidinyl complex [Pd(PPh<sub>3</sub>)(η<sup>1</sup>-C<sub>4</sub>H<sub>3</sub>N<sub>2</sub>)(η<sup>2</sup>-SS)], (<b>5</b>: SS = S<sub>2</sub>CNC<sub>4</sub>H<sub>8</sub>; <b>6</b>: SS = S<sub>2</sub>COEt) and η<sup>2</sup>-Tp η<sup>1</sup>-pyrimidinyl complex [Pd(PPh<sub>3</sub>)(η<sup>1</sup>-C<sub>4</sub>H<sub>3</sub>N<sub>2</sub>)(η<sup>2</sup>-Tp)], <b>7</b>, respectively. Treatment of <b>1</b> with AgBF<sub>4</sub> in acetonitrile at room temperature resulted in the formation of the doubly bridged η<sup>2</sup>-pyrimidinyl dipalladium complex [{Pd(PPh<sub>3</sub>)(CH<sub>3</sub>CN)}<sub>2</sub>(μ,η<sup>2</sup>-C<sub>4</sub>H<sub>3</sub>N<sub>2</sub>)<sub>2</sub>][BF<sub>4</sub>]<sub>2</sub>, <b>8</b>. All of the complexes were identified using spectroscopic methods, and complexes <b>3</b>, <b>4</b>, and<b> 8</b> were determined using single-crystal X-ray diffraction analyses.
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