Synthesis and structures of copper(I) complexes with phosphino-functionalized N-heterocyclic carbenes (NHCP) and Bis-N-heterocyclic carbenes (Bis-NHC)
New copper(I) complexes bearing N-phosphino- and N-phosphinomethyl-functionalized NHC ligands (NHCP systems) were synthesized and fully characterized. Using halide-containing copper(I) precursors, strikingly different structural motifs were found, dependent on the substitution pattern of the NHCP mo...
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| Main Authors: | , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
26 November 2012
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| In: |
Organometallics
Year: 2012, Volume: 31, Issue: 22, Pages: 8000-8011 |
| ISSN: | 1520-6041 |
| DOI: | 10.1021/om300701u |
| Online Access: | Verlag, Volltext: http://dx.doi.org/10.1021/om300701u Verlag, Volltext: https://doi.org/10.1021/om300701u 
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| Author Notes: | Erik Kühnel, Igor V. Shishkov, Frank Rominger, Thomas Oeser, and Peter Hofmann |
| Summary: | New copper(I) complexes bearing N-phosphino- and N-phosphinomethyl-functionalized NHC ligands (NHCP systems) were synthesized and fully characterized. Using halide-containing copper(I) precursors, strikingly different structural motifs were found, dependent on the substitution pattern of the NHCP moiety. An interesting tetranuclear μ4-bridged copper(I) cluster (4b) is formed when CuBr·SMe2 is reacted with the N-phosphino-substituted ligand 1a, whereas the dinuclear complex 4a is formed in an analogous reaction with 1b. Dinuclear metallacycles (2a,b) were isolated and characterized by X-ray diffraction when the halide-free copper(I) precursor [Cu(CH3CN)4]PF6 was reacted with NHCP ligands 1a,b using the N-phosphinomethyl-substituted NHCP ligands 5a,b, as well as employing the bis-NHC ligands BIM and BIM-BMe2 (10a,b), respectively. The observed copper(I)-copper(I) distances are directly correlated with the size of the metallacycle formed. An unexpected strong influence upon the metal-metal separation was found for the charged complexes in 10a,b. Using directly N-tBu-substituted NHCP ligands led to formation of an electronically less favorable trans-C,C coordination at the copper(I) centers (3 and 6a), which inhibited the formation of a dimeric species in the case of 3. |
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| Item Description: | Gesehen am 27.11.2018 |
| Physical Description: | Online Resource |
| ISSN: | 1520-6041 |
| DOI: | 10.1021/om300701u |