Solvent-Free Organometallic Migratory Insertion Reactions
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- 作者：Olalere G. Adeyemi and Neil J. Coville
- 刊名：Organometallics
- 出版年：2003
- 出版时间：May 26, 2003
- 年：2003
- 卷：22
- 期：11
- 页码：2284 - 2290
- 全文大小：104K
- 年卷期：v.22,no.11(May 26, 2003)
- ISSN：1520-6041
文摘
Migratory insertion reactions of organometallic complexes have been shown to occur inthe absence of solvent and, more significantly, between solid reagents. Reaction between(
ges/gifchars/eta.gif" BORDER=0 >5-C5H5)M(CO)3Me (M = Mo, W) or (ges/gifchars/eta.gif" BORDER=0 >5-C5H5)Fe(CO)2Me and PPh3 (no solvent) took placeat temperatures between 40 and 90 ges/entities/deg.gif">C and gave the products (ges/gifchars/eta.gif" BORDER=0 >5-C5H5)M(CO)2(PPh3)COMeand (ges/gifchars/eta.gif" BORDER=0 >5-C5H5)Fe(CO)(PPh3)COMe in moderate to good yield (60-99%). The Mo and Wcomplexes reacted in the solid state when T < 80 ges/entities/deg.gif">C. The decarbonylation of (ges/gifchars/eta.gif" BORDER=0 >5-C5H5)Mo(CO)2(PPh3)COMe to yield (ges/gifchars/eta.gif" BORDER=0 >5-C5H5)Mo(CO)2(PPh3)Me also occurred in the solid state(120 ges/entities/deg.gif">C). Reaction of (ges/gifchars/eta.gif" BORDER=0 >5-C5H5)Mo(CO)3Me with a range of ligands, L (L = PPh3, P(p-MeOC6H4)3, PCy3, PEt3, AsPh3, POPh3, P(OEt)3; 1:1 reagent ratio, 90 ges/entities/deg.gif">C, 15 min), in theabsence of solvent gave (ges/gifchars/eta.gif" BORDER=0 >5-C5H5)Mo(CO)2(L)COMe (7-100% yield) and, on extended reaction,(ges/gifchars/eta.gif" BORDER=0 >5-C5H5)Mo(CO)2(L)Me in varying yields. A kinetic study of the solid-state reaction between(ges/gifchars/eta.gif" BORDER=0 >5-C5H5)Mo(CO)3Me and PPh3 yielded rate constants, e.g. k = 5.18 × 10-5 s-1 (Mo:P = 1:10;50 ges/entities/deg.gif">C), which compares with the literature solution data in toluene (k = (0.8-2.5) × 10-5s-1, 50 ges/entities/deg.gif">C) using similar metal to ligand ratios. The data are consistent with a pseudo-first-order reaction in the presence of PPh3. Diffusional effects on the reaction rate are detectedat low temperature and low PPh3 ratios.