Substituent effects upon alkyl migration to coordinated CO. Syntheses and carbonylation studies of (CO)5MnCH2I and (CO)5MnCH2OSiMe3
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Iodide ICH2OSi(CH3)3 is generated in situ from H2C=O and (CH3)3SiI and then reacted with K+(CO)5Mn− to give α-(silyloxy)alkyl (CO)5MnCH2OSi(CH3)3 (1). Reaction of (CO)5MnSi(CH3)3 (3) with H2C=O does not yield 1, and the addition of (CH3)3SiI to (CO)5MnCH2OCH3 gives instead iodomethyl complex (C-O)5MnCH2I (2) and CH3OSi(CH3)3. While 1 is easily converted to acyl (CO)5MnCOCH2OSi(CH3)3 (7) under 200 psi of CO, 2 decomposes (to (CO)5MnI and/or [(CO)4MnI]2) faster than it carbonylates. The observed rates of carbonylation of 1 and reference alkyl (CO)5MnCH2OCH3 are first order and independent of CO pressure over the 750–1500 psi range in acetonitrile. Average kobsd at 24 °C are (10.9 ± 1.7) × 10−4 s−1 and (3.0 ± 0.5) × 10−4, respectively. Comparisons are made with the carbonylation rates of other (CO)5MnCH2X compounds. © 1982, American Chemical Society. All rights reserved.
author list (cited authors)
Brinkman, K. C., Vaughn, G. D., & Gladysz, J. A.