ChemInform Abstract: Reaction of Di‐ (IV) and Trialkylstannyl Chlorides (II) with Chloroamine (I) in an Aqueous Medium. Crystal Structure of N‐Chloro‐N‐ trimethylstannyl‐4‐chlorobenzenesulfonamide.

Abstract

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Observation of a Photogenerated Rh2 Nitrenoid Intermediate in C–H Amination

“…Such a transformation would reduce the Rh 2 fragment by one electron, and thus a Rh 2 [II,III] precursor is required to access the Rh 2 [II,II] nitrenoids that mediate Rh 2 -catalyzed C–H amination with iminoiodinanes . In contrast to the well-recognized facility of photochemical N–Cl homolysis in N -chloroamines to generate nitrogen-centered radicals (i.e., the Hofmann-Löffler-Freytag reaction), , the photochemistry of transition-metal-bound N -chloroamido ligands is less well explored . Here we report the synthesis of a Rh 2 N -chloroamide complex and demonstrate that photolysis of this compound unveils a reactive Rh 2 nitrenoid that participates in C–H amination.…”