Abstract
In the reaction of C 5H 5Mo(CO) 3Cl with pyridien-(2)-carboxylic acid thioamides the neutral C 5H 5Mo(CO) 2LL ★ complexes are obtained with LL ★ = ligand anion, coordinated by pyridine-N and thioamides-S with formation of a five-membered chelate ring. The uncoordinated thiomide nitrogen with only 2 substituents is basic and can be protonated. In contrast, the coresponding reactions with pyridine-(3)-carboxylic acid thioamides only give the C 5H 5Mo(CO) 2- thioamidato complexes containing a four-membered chelate ring with coordination via thioamide-N and thioamide-S. The (+) 436-and (−) 436-diastereoisomers of C 5H 5Mo(CO) 2LL ★ with opposite configuration at the molybdenum atom can be separated by chromatography, crystal picking or fractional crystallization. The (+) 436-and(−) 436-diastereoisomers, configurationally stable at room temperature, differ in their 1H NMR spectra. At 90° C in toluene solution starting from either isomer the equilibrium (+) 436/(−) 436 ( 58 42 ) is approached in a 1st order with a half life τ 1 2 of 9 min by change of configuration at the molybdenum atom.
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