Abstract
Nitric oxide (NO) insertion into a metalloporphyrin rhodium-carbon bond is observed when crystals of (TPP)Rh(C6H4Cl)(CH2Cl2) x (TPP = tetraphenylporphyrinato dianion) are exposed to NO gas over a two week period. The NO-inserted product was identified by X-ray crystallography as (TPP)Rh(ONC6H4Cl-o)(CH2Cl2)0.5 & centerdot;(TPP)Rh(C6H4Cl-p/m)(CH2Cl2)0.5, in which NO inserted selectively into the ortho-Cl aryl isomer but not into the para-/meta-Cl aryl isomers. Density functional theory calculations predict a higher reactivity for the ortho-Cl isomer and thus provide a rationale for the preferred NO insertion into the potentially more reactive ortho-Cl isomer under our reaction conditions. Whereas NO insertion reactions are well-known for coordination-organometallic compounds, this result represents the first such NO insertion into a metalloporphyrin metal-carbon bond for any metal.