The synthesis and properties of the transannularly bonded electron-rich olefin derived from 1,4,8,11-tetra-azacyclotetradecane; X-ray crystal structure of the chelating cis-dicarbenerhodium(I) salt obtained therefrom
- 1 January 1980
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Chemical Communications
- No. 24,p. 1180-1181
- https://doi.org/10.1039/c39800001180
Abstract
Reaction of 1,4,8,11-tetra-azacyclotetradecane with HC(OMe)2NMe2 yields the olefin (abbreviated as L2 cyclam), formed by filling the macrocyclic cavity with a transannularly bound CC bond, this being cleaved by (a) insertion therein of a RhI moiety upon treatment with [{Rh(cod)Cl}2](cod = cyclo-octa-1,5-diene) to furnish [Rh(cod)(L2 cyclam)][Rh(cod)Cl2](3), or (b) oxidation to give a bis(urea); X-ray analysis of the chelating dicarbenerhodium(I) complex, obtained from (3) and CO, to R= 0·0357, R′= 0·0716, shows Rh–C(carb, av.) 2·02 and Rh–(cod)av 2·20 Å, and C(carb)–Rh–C(carb′)= 78·1(2)°.Keywords
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