LEE, YA CHUNG, YK KIM, Y JEONG, JH CHUNG, G LEE, D 2024-01-21T23:40:19Z 2024-01-21T23:40:19Z 2022-01-11 1991-10 0276-7333 https://pubs.kist.re.kr/handle/201004/146727 [{N(CH2CH2O)3SiC6H5}Mn(CO)3]ClO4 (1) undergoes regioselective reaction with RMgBr (R = Ph, Me, Et) in CH2Cl2 to give [eta-5-1-(N(CH2CH2O)3Si)-6-(R)C6H5]Mn(CO)3 (2a, R = Ph; 2b, R = Me; 2c, R = Et), with EtLi in THF to yield [eta-5-2-(N(CH2CH2O)3Si)-6-(R)C6H5]Mn(CO)3 (3c, R = Et), and with RMgBr (R = Ph, Me, Et), LiCH2CO2CMe3, LiCH2CN, and Li activated CHS(CH2)3S in THF to yield [eta-5-3-(N(CH2CH2O)3Si)-6-(R)C6H5]Mn(CO)3 (4a, R = Ph; 4b, R = Me; 4c, R = Et; 4e, R = CH2CO2CMe3; 4j, R = CH2CN; 4k, R = activated CHS(CH2)3S). However, 1 does not react regioselectively with the carbanions from isobutyronitrile, acetone, or tert-butyllithium or with sodium cyanide. The selectivity of the nucleophilic addition to 1 is strongly dependent on the nucleophile and reaction medium. The structure of 2a has been confirmed by X-ray diffraction: space group P1BAR; a = 9.169 (2) angstrom, b = 9.905 (2) angstrom, c = 12.353 angstrom, alpha = 110.25 (2)-degrees, beta = 97.33 (1)-degrees, gamma = 97.70 (2)-degrees; final error indices R = 0.042, R(G) = 0.043 for 2856 unique data with I > 3-sigma(I). English AMER CHEMICAL SOC CARBANION ATTACK COMPLEXES ARENE AZASILATRANES REGIOSELECTIVITY SYNTHESIS AND REACTIVITY OF (PHENYLSILATRANE)MANGANESE TRICARBONYL PERCHLORATE - MOLECULAR-STRUCTURE OF [(ETA-5-1-N(CH2CH2O)3SI-6-PHC6H5)MN(CO)3] Article 10.1021/om00056a049 1 ORGANOMETALLICS, v.10, no.10, pp.3707 - 3713 ORGANOMETALLICS 10 10 3707 3713 scie scopus A1991GK14300049 2-s2.0-0001414192 Chemistry, Inorganic & Nuclear Chemistry, Organic Chemistry Article CARBANION ATTACK COMPLEXES ARENE AZASILATRANES REGIOSELECTIVITY