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Bulky β-Diketones Enabling New Lewis Acidic Ligand Platforms
- Source :
- Inorganic chemistry. 56(19)
- Publication Year :
- 2017
-
Abstract
- The synthesis of a sterically encumbered β-diketone ligand (Aracac) substituted with 2,6-(2,4,6-Me3C6H2)2C6H3 is described. Coordination complexes of the type M(Aracac)2Cl(solv) (M = Ti, V, Cr; solv = THF, CH3CN) were prepared by the reaction of Aracac with MCl3 (M = V, Cr) or with TiCl4 to generate Ti(Aracac)2Cl2, followed by reduction. These complexes show a trend of alternating the cis/trans geometric preference with increasing dn electron count (n = 0, 1, 2, 3), which is rationalized in part by the unusual ability of β-diketonates to behave as either a weak π donor or a π acceptor in the cis and trans geometries, respectively. In this way, the bis-β-diketonate platform can accommodate the varying electronic demands of the coordinated metal ion. These results demonstrate the ability to limit the coordination of β-diketonates on metal complexes for the first time, providing a chemically robust and coordinatively versatile platform for mechanistic investigations, metal functionalization, and improved cat...
- Subjects :
- Steric effects
010405 organic chemistry
Ligand
Chemistry
Stereochemistry
010402 general chemistry
01 natural sciences
Acceptor
0104 chemical sciences
Inorganic Chemistry
Metal
Crystallography
visual_art
visual_art.visual_art_medium
Surface modification
Physical and Theoretical Chemistry
Cis–trans isomerism
Subjects
Details
- ISSN :
- 1520510X
- Volume :
- 56
- Issue :
- 19
- Database :
- OpenAIRE
- Journal :
- Inorganic chemistry
- Accession number :
- edsair.doi.dedup.....9a8d1330ff8033c3fd121ca6a6905427