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Structural Diversity of Calcium Organocuprates(I): Synthesis of Mesityl Cuprates via Addition and Transmetalation Reactions of Mesityl Copper(I)
Author(s) -
Krieck Sven,
Görls Helmar,
Westerhausen Matthias
Publication year - 2010
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200900552
Subject(s) - transmetalation , chemistry , cuprate , copper , solvent , toluene , medicinal chemistry , organic chemistry , catalysis , materials science , optoelectronics , doping
The addition of [(L) 4 Ca(I)Mes] (Lewis base L=thf, Et 2 O) to mesityl copper(I) and the transmetalation reaction of mesityl copper(I) with activated calcium are suitable pathways for the synthesis of dimesityl cuprates(I) of calcium. However, the structures of the calcium cuprates(I) depend on the preparative procedure. The transmetalation reaction leads to the formation of [Mes‐Cu‐Mes] − anions whereas the addition yields dinuclear [(Mes‐Cu) 2 (μ‐Mes)] − anions. The solvent‐separated counterions are [Ca(thf) 6 ] 2+ and [(thf) 5 CaI] + , respectively. In contrast to these findings, the addition of [(L) 4 Ca(I)Mes] to mesityl copper(I) in an Et 2 O/toluene mixture led to formation of tetrameric solvent‐free iodocalcium dimesityl cuprate(I) [ICa(μ‐η 1 ,η 6 ‐Mes 2 Cu)] 4 , representing a rare example of a heavy Normant‐type organocuprate.