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)

[η_5-OH_3C(O)C_5H_4Cr(CO)_2]_2S 1, [η~5-CH_3O_2CC_5H_4Cr(CO)_2]_2S 2 and [η~5-C_2H_5O_2CC_5H_4Cr(CO)_2]_2S 3 were prepared by the reactions of corresponding sodium salts of functional η~5-cyclopentadienyl-tricarbonylchromium anions with SOCl_2. Reduction of 1 with NaBH_4 prdouced [η~5-CH_3CH(OH)C_5H_4Cr(CO)_2]_2S 4, while saponification of 2 followed by acidification and recrystallization from acetone afforded [η~5-HO_2CC_5H_4Cr(CO)_2]_2S·nCH_3C·(O)CH_3 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 η~5-CH_3C(O)C_5H_4Cr(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(?).