Synthesis, Reaction and Structures of Functionally Substituted η~5-Cyclopentadienyl Compounds With Cr≡S Triple Bond η~5-RC_5H_4Cr(CO)_2_2S (R=CH_3C(O),CH_3O_2C,C-2H_5O_2C,CH_3CH(OH),CO_2H)

摘要

[η5-OH3C（O）C5H4Cr（CO）2]2S 1, [η5-CH3O2CC5H4Cr（CO）2]2S 2 and [η5-C2H5O2CC5H4Cr（CO）2]2S 3 were prepared by the reactions of corresponding sodium salts of functional η5-cyclopentadienyl-tricarbonylchromium anions with SOCl2. Reduction of 1 with NaBH4 prdouced [η5-CH3CH（OH）C5H4Cr（CO）2]2S 4, while saponification of 2 followed by acidification and recrystallization from acetone afforded [η5-HO2CC5H4Cr（CO）2]2S·nCH3C·（O）CH3 5. 1—5 are a new class of Cr≡S triple bond compounds containing functional organic group on the cyclopentadienyl ring. A single-crystal X-ray diffraction analysis of 1 revealed that it consists of two identical organometallic fragments η5-CH3C（O）C5H4Cr（CO）2 joined together by a sulfur atom via triple bonds. The geometry of structural unit Cr≡S≡Cr belongs to linearity and the average triple bond length of Cr≡S is 2.072（?）.