Formation of Coordinated RZn(macrocycle)+ Cations and Organozincate Anions from Reactions of Organozinc Compounds and Macrocycles

• Published in: Organometallics 2001-09, Vol.20 (19), p.4018-4023
• Main Authors: Fabicon, Ronaldo M, Richey, Herman G
• Format: Article
• Language: English
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om0102798

An RZnZ compound (R = alkyl) and a macrocycle react in benzene to form RZn(macrocycle)+ ions when the macrocycle is an effective coordinator for RZn+ and Z- can exist as the anion or become attached to an organometallic acceptor to form an organometalate anion. R2Zn and R3Al form RZn(macrocycle)+R4Al- with 14N4 (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), 15N5 (1,4,7,10,13-pentamethyl-1,4,7,10,13-pentaazacyclopentadecane), 2,1,1-cryptand, or 2,2,1-cryptand but not with 1,4,7,10,13,16-hexamethyl-1,4,7,10,13,16-hexaazacyclooctadecane, 2,2,2-cryptand, 15-crown-5, or 18-crown-6. RZnZ, R2Zn, and 14N4 form RZn(14N4)+R2ZnZ- when Z is Cl, Br, I, or 3,5-di-tert-butylphenoxy but not when Z is tert-butoxy. Various combinations of RZnZ with Z = Cl, Br, I, 2,6-di-tert-butylphenoxy, or 3,5-di-tert-butylphenoxy and 14N4, 15N5, 2,1,1-cryptand, or 2,2,1-cryptand form RZn(macrocycle)+Z- solids; solids do not form when Z is methoxy or tert-butoxy nor when the macrocycle is 12-crown-4, 15-crown-5, or 18-crown-6.