Half-open ruthenocenes derived from [Ru(C5Me5)Cl]4: Syntheses, characterizations, and solid-state structures

Article abstract of DOI:10.1021/om00040a045

A variety of half-open ruthenocenes of the general formula Ru(C₅Me₅)(Pdl) have been prepared from [Ru(C₅Me₅)Cl]₄. For C₅H₇ or alkylated or arylated pentadienyl groups (1-, 2-, or 3-C₆H₉; 2,3-C₇H₁₁; 2,4-C₇H₁₁; 1,5-(C₆H₅)₂C₅H₅), their introductions were brought about by using their potassium salts. For the oxo dienyl analogues 2,4-OC₆H₉ or 3,5-OC₆H₉, the respective enone or enal could be utilized, which underwent deprotonation upon coordination in the presence of K₂CO₃. With HPdl = 2,4-(CF₃)₂C₅H₆, coordination is accompanied by the spontaneous elimination of HCl, yielding Ru(C₅Me₅)[2,4-(CF₃)₂C ₅H₅]. A similar reaction led to Ru(C₅Me₄Et)[2,4-(CF₃)₂C ₅H₅]. In addition to various spectroscopic studies, structural studies were carried out on the Pdl = 3-C₆H₉ and 3,5-OC₆H₉ complexes, as well as for Ru(C₅Me₄Et)[2,4(CF₃)₂C ₅H₅]. For the Pdl = 3-C₆H₉ complex, the space group is P2₁/m with a = 7.598 (1) ?, b = 13.246 (2) ?, c = 7.526 (1) ?, β = 96.429 (4)°, and V = 752.7 ?³ for Z = Z. For the oxo dienyl compound, the space group is P2₁2₁2₁, with a = 10.651 (2) ?, b = 11.925 (1) ?, c = 11.987 (2) ?, and V = 1522.4 ?³ for Z = 4. For the 2,4-(CF₃)₂C₅H₅ compound, the space group is CmC2₁ with a = 15.324 (3) ?, b = 8.785 (2) ?, c = 13.726 (2) ?, and V = 1847.8 ?³ for Z = 4. The structures were refined to respective R (and R_w) values of 0.026 (0.030), 0.034 (0.035), and 0.028 (0.031).