The alkyl nitrite complexes [Ru(bpy)2(py)N(O)OR]2+ (bpy = 2,2′-bipyridine; py = pyridine; R = methyl, ethyl, n-butyl, isopropyl) have been prepared by reactions involving attack of the corresponding alkoxide ions on the nitrosyl nitrogen in [Ru(bpy)2(py)NO]3+. In the products the alkyl nitrite groups appear to be N bound. From the properties of the complexes, it seems that dπ(RuII) → π*(N(O)OR) back-bonding is significant and that the alkyl nitrite group is a better π-electron acceptor than the nitro, pyridyl, or acetonitrile groups when bound to Ru(II). The complexes form in dry acetonitrile when both alcohol and base (collidine) are added, Ru(bpy)2(py)NO3+ + ROH + B → Ru(bpy)2(py)N(O)OR2+ + BH+, and the reversible nature of the chemistry is seen following the addition of excess acid, Ru(bpy)2(py)N(O)OR2+ + H+ → Ru(bpy)2(py)NO3+ + ROH. Once formed, the alkyl nitrite complexes undergo an irreversible, one-electron oxidation (at ∼+1.75 V vs. SSCE) and the major products are [Ru(bpy)2(py)NO]3+ and ROH. The chloro analogues [Ru(bpy)2(Cl)N(O)OR]+ (R = ethyl, isopropyl) have also been prepared, in this case by attack of RO- on [Ru(bpy)2(Cl)NO]2+. It has proven difficult to characterize the complexes fully, but they appear to have properties similar to those found for the pyridyl complexes.
|Number of pages||5|
|Publication status||Published - 1980|
ASJC Scopus subject areas
- Inorganic Chemistry