Cyclopropenylgold(I) complexes as aurated carbenoids or quasi-carbenes
Highly strained hydrocarbons have always been a research target of high interest. Due to their untypical electronic structure, they show interesting reactivity patterns and can easily be activated by π-coordination to or insertion reactions with metal complexes. Herein we report the synthesis of a r...
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| Main Authors: | , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
2018
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| In: |
Advanced synthesis & catalysis
Year: 2018, Volume: 360, Issue: 9, Pages: 1810-1821 |
| ISSN: | 1615-4169 |
| DOI: | 10.1002/adsc.201701526 |
| Online Access: | Verlag, Volltext: http://dx.doi.org/10.1002/adsc.201701526 Verlag, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/adsc.201701526 
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| Author Notes: | Florian F. Mulks, Patrick W. Antoni, Frank Rominger, A. Stephen K. Hashmi |
| Summary: | Highly strained hydrocarbons have always been a research target of high interest. Due to their untypical electronic structure, they show interesting reactivity patterns and can easily be activated by π-coordination to or insertion reactions with metal complexes. Herein we report the synthesis of a range of 3,3-disubstituted cyclopropenylgold(I) complexes. The synthesis of such compounds with a metal, which usually easily activate cyclopropenes is a double-edged sword. We found σ-bound vinylic gold to generally have a strong stabilizing effect in terms of ring strain. The complexes show a strong distortion, preactivating the cyclopropenyls towards the ring-opening mode which thermally generates 1-aurated vinylcarbenes which is reflected by a much faster conversion (Ea of 10 kcal/mol instead of 40 kcal/mol, the reaction proceeds at temperatures as low as −20 °C instead of 200 °C reported in the literature). In 3-phenyl-cyclopropenyl complexes, these could be trapped intramolecularly to give indenylgold(I) complexes. The properties of these highly strained complexes were investigated, utilizing a range of analytical and experimental procedures and Kohn-Sham density functional theoretic methods. |
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| Item Description: | Published online: March 9, 2018 Gesehen am 28.06.2018 |
| Physical Description: | Online Resource |
| ISSN: | 1615-4169 |
| DOI: | 10.1002/adsc.201701526 |