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Pentamethylcyclopentadienyl ruthenium dichloride dimer

Pentamethylcyclopentadienyl ruthenium dichloride is an organoruthenium chemistry with the formula [(C<sub>5</sub>(CH<sub>3</sub>)<sub>5</sub>)RuCl<sub>2</sub>]<sub>2</sub>, commonly abbreviated [Cp*RuCl<sub>2</sub>]<sub>2</sub>. This brown paramagnetic solid is a reagent in organometallic chemistry. It is an unusual example of a compound that exists as isomers that differ in the intermetallic separation, a difference that is manifested in a number of physical properties.

Preparation, structure, reactions

The compound has C<sub>2h</sub> symmetry, with each metal atom having pseudo-octahedral geometry. In the crystal structure, two isomers are observed in the unit cell, one with a 2.93&nbsp;àruthenium–ruthenium bond and the other with a long internuclear distance of 3.75&nbsp;Å. The former isomer is diamagnetic, and the latter is magnetic.

It is prepared by the reaction of hydrated ruthenium trichloride with pentamethylcyclopentadiene.

2 Cp*H + 2 RuCl<sub>3</sub>·3H<sub>2</sub>O → [Cp*RuCl<sub>2</sub>]<sub>2</sub> + 2 HCl + 6 H<sub>2</sub>O

The reaction is accompanied by formation of decamethylruthenocene.

Pentamethylcyclopentadienyl ruthenium dichloride can reduced to the diamagnetic tetramer of Ru(II):

2 [Cp*RuCl<sub>2</sub>]<sub>2</sub> + 2 Zn → [Cp*RuCl]<sub>4</sub> + 2 ZnCl<sub>2</sub>

Methoxide also can be used to produce a related diruthenium(II) derivative, which is also diamagnetic:

[Cp*RuCl<sub>2</sub>]<sub>2</sub> + 3 NaOCH<sub>3</sub> + HOCH<sub>3</sub> → [Cp*RuOCH<sub>3</sub>]<sub>2</sub>] + 3 NaCl + CH<sub>2</sub>O + HCl

Treating the tetramer with 1,5-cyclooctadiene in etheral solvent gives the mononuclear complex chloro(1,5-cyclooctadiene)(pentamethylcyclopentadienyl)ruthenium(II).

0.25 [Cp*RuCl]<sub>4</sub> + 1,5-cyclooctadiene → Cp*RuCl(1,5-cyclooctadiene)

Compounds like Cp*RuCl(1,5-cyclooctadiene), the tetramer [Cp*RuCl]<sub>4</sub>, and related diamagnetic Cp*Ru(III) complexes have been investigated as hydrogenation catalysts.

See also

References