ChemInform Abstract: Ruthenium Complexes with Diazadienes. Part 9. A New Chromophore from Two Diazadiene Ruthenium Units. Structure and Properties of ((CO)2(DAD)CH3Ru-RuCH3(DAD)(CO)2) (DAD: iPr-N=CH-CH=N-iPr).
Abstract
The two-electron reduction of diiododicarbonyl(diazadiene)-Ru(II) complexes such as (I) gives the reactive ruthenates(0) of the type ((diazadiene)Ru(CO)2I)- which add organic electrophiles to afford iodo(organyl)-Ru compounds of the type (III) as demonstrated for the example (IIIa).
ChemInform Abstract
The two-electron reduction of diiododicarbonyl(diazadiene)-Ru(II) complexes such as (I) gives the reactive ruthenates(0) of the type ((diazadiene)Ru(CO)2I)- which add organic electrophiles to afford iodo(organyl)-Ru compounds of the type (III) as demonstrated for the example (IIIa). Attempts to prepare trimethylsilyl analogues using CF3SO3SiMe3 in THF result in the formation of the siloxybutyl derivatives (IIIc) and (IIIe) as the main products in addition to (IIId). The electrochemical behavior of (III) depends on the steric requirements of the diazadiene involved. With a small diazadiene (R1: iPr) the one-electron reduction e.g. of (IIIa) gives a Ru(I) intermediate which finally yields a stable Ru-Ru bonded dimer (IV). With a bulky diazadiene (R1: CH(iPr)2) the reduction e.g. of (IIIb) proceeds to the organoruthenates(0) (V). The structure of the title dimer (IV) (space group F2dd, Z = 8) is determined by X-ray analysis.
