Koordinationschemie perhalogenierter Cyclopentadiene und Alkine, XI [1].<br />Darstellung einiger Cymantrenyl-mono- und bis-thioether mit einer weiteren funktionellen Gruppe am Cyclopentadienylring. Molekülstruktur von [C₅Cl₂(SMe)₂(PPh₂)]Mn(CO)₃ / Coordination Chemistry of Perhalogenated Cyclopentadienes and Alkynes, XI [1]<br />Synthesis of Some Cymantrene Mono- and Bis-Thioethers with One Additional Functional Group on the Cyclopentadieny

Abstract

M ultifunctional Cymantrene Thioethers, Organometallic P -S -C h elate Ligand, Chiral Cyclopentadienyl Complexes, Crystal StructureThe reaction o f [C5Cl4(SM e)]M n(CO)3 (la ) with «-butyllithium and the electrophiles SiM e3Cl, C 0 2, or PPh,Cl regiospecifically yields the chiral 1, , 7 a , Ph, 7b) can be obtained. The crystal structure determination o f 7a (C " H 160 3PS-,CLMn, m onoclinic, P 2,/c, a = 18.714(6) A, b = 9.506(3) A, c = 14.475(3) A, ß = 109.18(2)°, V = 2432.1(12) A \ Z = 4) shows an orientation o f the neighbouring PPh2-and SMe groups, that allows chelation o f an additional metal fragment. 3-disubstituted functional cym an trene thioethers [C5Cl3(SM e)R]M n(CO )3 (R = SiM e3 (2), COOLi (3a), PPh2 (4)). 3 a can be protonated to give the corresponding carboxylic acid (3 b), which in turn can be transformed to the acid chloride [C5Cl3(SM e)(COCl)]M n(CO)3 (3c). 3c reacts with N a N 3 to yield after work-up the urea derivative O C [[N H -C 5Cl3(SM e)]M n(CO)3]2 (3d). U sing the cymantrene bisthioethers [C5Cl3(SR )2]M n(CO)3 (R = Me, 5a, Ph, 5b) as starting materials, the carboxyl de rivatives [C5Cl2(SM e)2(COR)]M n(CO)3 (R = OLi, 6a, OH, 6b, Cl, 6 c) and the potential organometallic S,P-chelate ligands [C5Cl2(SR)2(PPh2)]M n(CO)3 (R = Me