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. 2017 Oct 1;8(10):7174-7179.
doi: 10.1039/c7sc02986a. Epub 2017 Aug 24.

A β-Carbon elimination strategy for convenient in situ access to cyclopentadienyl metal complexes

G Smits  1 , B Audic  1 , M D Wodrich  2 , C Corminboeuf  2 , N Cramer  1
Affiliations

A β-Carbon elimination strategy for convenient in situ access to cyclopentadienyl metal complexes

G Smits et al. Chem Sci. .

Abstract

The electronic and steric properties of tailored cyclopentadienyl (Cp) ligands are powerful handles to modulate the catalytic properties of their metal complexes. This requires the individual preparation, purification and storage of each ligand/metal combination. Alternative, ideally in situ, complexation protocols would be of high utility. We disclose a new approach to access Cp metal complexes. Common metal precursors rapidly react with cyclopentadienyl carbinols via β-carbon eliminations to directly give the Cp-metal complexes. An advantage of this is the direct and flexible use of storable pre-ligands. No auxiliary base is required and the Cp complexes can be prepared in situ in the reaction vessel for subsequent catalytic transformations.

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Figures

Scheme 1
Scheme 1. Generation of organometallics using the β-carbon elimination strategy.
Scheme 2
Scheme 2. (a) Synthesis of Cp pre-ligand carbinols 2. (b) Envisioned β-C elimination to access Cp*Rh(i) complexes.
Fig. 1
Fig. 1. Reaction profile of the β-C elimination of carbinol 2m.
Fig. 2
Fig. 2. (a) Complexation rates of different carbinols 2; yields of 4a after 60 min: 2d: 22%; 2h: 82%; 2m: 99%; 2p: 99%; 2q: 75%. (b) Reaction profiles of carbinols 2 during complexation.
Scheme 3
Scheme 3. In situ Cp metal complex preparation and direct application in Rh(iii), Rh(i) and Ir(iii) catalysis. PMP = 4-methoxyphenyl.
See this image and copyright information in PMC

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