TY - JOUR
T1 - Mehrfachbindungen zwischen hauptgruppenelementen und übergangsmetallen. XVII. Selen- und tellur-brücken in organometallkomplexen
T2 - AUFBAU, protonierung und methylierung
AU - Herrmann, Wolfgang A.
AU - Rohrmann, Jürgen
AU - Hecht, Christian
PY - 1985/7/16
Y1 - 1985/7/16
N2 - Selenium acts as a bridging ligand between two iron atoms in the novel complex (μ-Se)(η5-C5H5)Fe(CO)2]2 (1), obtained in 60% yield from Na+[(η5-C5H5)Fe(CO)2] and Se2Cl2. 1 displays nucleophilic reactivity towards protic acids (e.g., HBF4·OEt2) and methyl triflate, CF3SO3CH3, thus giving the protonated and methylated ionic species [(μ-SeR)(η5-C5H5)Fe(CO)22]+ (R = H: 2a, BF4 salt; R = CH3: 2b, PF6 salt) in quantitative yields. Rapid deprotonation of 2a occurs in the presence of bases such as diethylamine. Analogous protonation and methylation reactions have been observed with the tellurium complex (μ-Te)[(η5-C5H5)Cr(CO)3]2 (3); the ionic compounds [(μ-TeH)(η5-C5H5)Cr(CO)32]BF4 (4a) and [(μ-TeCH3) (η5-C5H5)Cr(CO)32]PF6(4a), respectively, are obtained. In contrast, the electron-deficient tellurium ligand of the manganese complex (μ3-Te)[(η5-C5H5)Mn(CO)2]3 (5) is neither attacked by Brønsted acids nor by electrophilic methylating agents (e.g., CF3SO3CH3) but is rather methylated by methyllithium to give the anionic species [(μ3-TeCH3)η5-C5H5)Mn(CO)23]- that can be isolated pure as the PPN+ salt 6.
AB - Selenium acts as a bridging ligand between two iron atoms in the novel complex (μ-Se)(η5-C5H5)Fe(CO)2]2 (1), obtained in 60% yield from Na+[(η5-C5H5)Fe(CO)2] and Se2Cl2. 1 displays nucleophilic reactivity towards protic acids (e.g., HBF4·OEt2) and methyl triflate, CF3SO3CH3, thus giving the protonated and methylated ionic species [(μ-SeR)(η5-C5H5)Fe(CO)22]+ (R = H: 2a, BF4 salt; R = CH3: 2b, PF6 salt) in quantitative yields. Rapid deprotonation of 2a occurs in the presence of bases such as diethylamine. Analogous protonation and methylation reactions have been observed with the tellurium complex (μ-Te)[(η5-C5H5)Cr(CO)3]2 (3); the ionic compounds [(μ-TeH)(η5-C5H5)Cr(CO)32]BF4 (4a) and [(μ-TeCH3) (η5-C5H5)Cr(CO)32]PF6(4a), respectively, are obtained. In contrast, the electron-deficient tellurium ligand of the manganese complex (μ3-Te)[(η5-C5H5)Mn(CO)2]3 (5) is neither attacked by Brønsted acids nor by electrophilic methylating agents (e.g., CF3SO3CH3) but is rather methylated by methyllithium to give the anionic species [(μ3-TeCH3)η5-C5H5)Mn(CO)23]- that can be isolated pure as the PPN+ salt 6.
UR - https://www.scopus.com/pages/publications/0002438989
U2 - 10.1016/0022-328X(85)80148-0
DO - 10.1016/0022-328X(85)80148-0
M3 - Artikel
AN - SCOPUS:0002438989
SN - 0022-328X
VL - 290
SP - 53
EP - 61
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1
ER -