Pentachlorocyclopentadienyl derivatives of manganese and rhodium

Article abstract of DOI:10.1021/ic50153a022

Reaction of diazotetrachlorocyclopentadiene, I, with di-μ-chloro-bis(1,5-cyclooctadienerhodium), [RhCl(1,5-C₈H₁₂)]₂, gives high yields of (η⁵-pentachlorocyclopentadienyl)(1,5-cyclooctadiene)rhodium, Rh(η⁵-C₅Cl₅)(COD), II. A similar reaction between I and pentacarbonylchloromanganese, MnCl(CO)₅, gave two products: pentacarbonyl(η¹-pentachlorocyclopentadienyl)manganese, Mn(η¹-C₅Cl₅)(CO)₅, III, and tricarbonyl(η⁵-pentachlorocyclopentadienyl)manganese, Mn(η⁵-C₅Cl₅)(CO)₃, IV. III is the first transition metal complex containing a η¹-C₅Cl₅^- ring and for which there is no analog in C₅H₅^--Mn chemistry. These compounds and other polychloro-substituted cyclopentadienyl complexes have been characterized by infrared, Raman, ¹³C nuclear magnetic resonance, and ³⁵Cl nuclear quadrupole resonance spectroscopy. Qualitative results from investigations into the mechanism of the insertion reactions of diazocyclopentadienes into manganese-halogen bonds are discussed.