Mono‐, Bis‐ and Tris(cyclopentadienyl) Compounds ‐ Syntheses of New Polydentate Ligands and their Molybdenum and Tungsten Complexes

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Abstract
Condensation reactions of cyclopentadienyl‐substituted chlorosilanes CpSiMe2Cl (Cp = C5H5, C5HMe4) with a number of phenols [C6H5OH, 1,3‐C6H4(OH)2, 1,4‐C6H4(OH)2, 1,3,5‐C6H3(OH)3] in the presence of excess base led to six novel molecules containing up to three cyclopentadienyl groups {e.g. 1,3,5‐C6H3[OSiMe2(C5Me4H)]3). The dynamic behavior of 1,4‐C6H4[OSiMe2(C5H5)]2 (2) was investigated by temperature‐variable 1H NMR and the reaction rate of the degenerate 1,2‐silicon shift determined. C6H5OSiMe2(C5H5) (1) and (2) were treated with NaH, (MeCN)3M(CO)3 (M = Mo, W), and Mel to give the η5‐complexes C6H6OSiMe2—(C5H4)M(CO)3Me (8: M = Mo, 9: M = W) and 1,4‐C6H4[OSiMe2‐(C5H4)M(CO)3Me]2 (10: M = Mo, 11: M = W) in good yields. The X‐ray crystal structure of 11 was determined.