Synthesis of Neutral and Anionic Tetranuclear Clusters\n[Pt<sub>4</sub>(μ<sub>2</sub>-PPh<sub>2</sub>)<sub>3</sub>{μ<sub>3</sub>-PPh(1,2-η<sup>2</sup>-Ph)-κ<sup>3</sup><i>P</i>}(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>L] and\n[NBu<sub>4</sub>][Pt<sub>4</sub>(μ<sub>2</sub>-PPh<sub>2</sub>)<sub>3</sub>{μ<sub>3</sub>-PPh(1,2-η<sup>2</sup>-Ph)-κ<sup>3</sup><i>P</i>}(C<sub>6</sub>F<sub>5</sub>)<sub>5</sub>]\nContaining Five Coordinate P Atoms and Two Pt−Pt\nBonds<sup>§</sup>
Ester Alonso (2355991)Juan Forniés (2440423)Consuelo Fortuño (2539663)Antonio Martín (133724)A. Guy Orpen (1287909)
Abstract
The reaction of [NBu<sub>4</sub>]<sub>2</sub>[(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>Pt(μ-PPh<sub>2</sub>)<sub>2</sub>Pt(μ-PPh<sub>2</sub>)<sub>2</sub>Pt(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>] with <i>cis</i>-[Pt(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>(thf)<sub>2</sub>]\n(molar ratio 1:2) in CH<sub>2</sub>Cl<sub>2</sub> gives [NBu<sub>4</sub>]<sub>2</sub>[Pt<sub>2</sub>(μ-C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>] and [NBu<sub>4</sub>][Pt<sub>4</sub>(μ-PPh<sub>2</sub>)<sub>4</sub>(C<sub>6</sub>F<sub>5</sub>)<sub>5</sub>]\n(<b>4</b>). Its molecular X-ray structure reveals that it is a tetranuclear complex with two Pt−Pt\nbonds and an unusual μ<sub>3</sub>-PPh<sub>2</sub> ligand, which has a η<sup>2</sup>-phenyl interaction with one of the\nplatinum centers. Complex <b>4 </b>reacts with HClO<sub>4</sub> to form [Pt<sub>4</sub>(μ-PPh<sub>2</sub>)<sub>4</sub>(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>], <b>5</b>, which\ncontains three Pt−Pt bonds and a μ<sub>3</sub>-PPh<sub>2</sub> bridging ligand. <b>5</b> reacts with L (L = PPh<sub>3</sub>, py)\nto yield the neutral [Pt<sub>4</sub>(μ-PPh<sub>2</sub>)<sub>4</sub>(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub> L] (<b>6</b> and <b>7</b>), with structures similar to <b>4</b>.
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