Allyl and Dienyl Complexes of Ruthenium

Submitted by ALBRECHT SALZER, ANDRE BAUER, STEFAN GEYSER, and FRANK PODEWILS  

RuCls MH2O is a nonstoichiometric material that may differ from one supplier to the other. The complex [Ru(H20)6] is in some cases an alternative precursor, but is difficult to prepare. We wish to present an improved synthesis of di-/i-chloro(dichloro)bis(77 77 -2,7-dimethylocta-2,6-diene-l,8-diyl)diruthenium and its application as a versatile precursor for Ru(ll) complexes with 77 -dienyl ligands.  

All compounds are routinely handled and stored under nitrogen in Schlenk flasks, although most solids can be handled safely in air. Solvents are dried and degassed before use. 

DI- -CHLORO(DICHLORO)BIS(i/ i/ -2,7-DIMETHYLOCTA-2,6-DIENE-l,8-DIYL) DIRUTHENIUM, Ru(i/ i/ -CioHi6)Cl2 2 

A solution of 18 g (68 mmol) of commercial ruthenium trichloride hydrate (Johnson Matthey, 40 3% ruthenium) in a mixture of isoprene (680 mL) and 2-methoxyethanol (280 mL) is heated at reflux for 10 days under inert gas (nitrogen or argon). The purple crystalline product is collected in a medium-porosity sintered-glass funnel, washed with diethyl ether, and dried in vacuo yield 19.9 g (95%). 

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