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Nucleophilic Additions to Allenylidene Ruthenium Complexes
No full textAllenylidene
complexes [RuÂ(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)Â(î»Cî»Cî»CPh<sub>2</sub>)Â{PÂ(OR)<sub>3</sub>}Â(PPh<sub>3</sub>)]Â[PF<sub>6</sub>] (R = Et (<b>1</b>), Me (<b>2</b>)) have been
synthesized by the reaction of the complexes [RuÂ(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)ÂClÂ{PÂ(OR)<sub>3</sub>}Â(PPh<sub>3</sub>)] with 1,1-diphenyl-2-propyn-1-ol in the presence of NaPF<sub>6</sub>. Addition of different nucleophiles to complex <b>1</b> allows
the synthesis of new allenyl or alkynyl ruthenium complexes depending
on the regiochemistry of the reaction. Unexpected complexes [RuÂ(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)Â{Îș<sup>3</sup>(<i>C,C,C</i>)-CÂ(R<sub>2</sub>PCH<sub>2</sub>CHî»CH<sub>2</sub>)î»Cî»CPh<sub>2</sub>}Â{PÂ(OEt)<sub>3</sub>}]Â[PF<sub>6</sub>] (R = <i><sup>i</sup></i>Pr (<b>9a</b>),
Ph (<b>9b</b>)), containing an unusual Îș<sup>3</sup>(<i>C,C,C</i>)<i>-</i>ligand have been obtained from the
reaction of the allenylidene complex <b>1</b> with alkenylphosphane
Ph<sub>2</sub>PCH<sub>2</sub>CHî»CH<sub>2</sub> (ADPP) or <i><sup>i</sup></i>Pr<sub>2</sub>PCH<sub>2</sub>CHî»CH<sub>2</sub> (ADIP). The formation of these complexes is proposed to proceed
through an intermediate, [RuÂ(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)Â(î»Cî»Cî»CPh<sub>2</sub>)Â{PÂ(OR)<sub>3</sub>}Â{Îș<sup>1</sup>(<i>P</i>)-R<sub>2</sub>PCH<sub>2</sub>CHî»CH<sub>2</sub>}]Â[PF<sub>6</sub>]
