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Diastereomeric molybdenum complexes (1A) and (1B) are formed from CpMo(CO)3Cl and the corresponding (S)-amidine. Complexes of type (1) are catalytically active. Knowledge gained in the case of (1A) (X-ray structure analysis) should permit a controlled influence of optically active 1-phenylalkyl substituents on the coordination sites adjacent to the chelate ring in other amidinato complexes.