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- Title
Synthesis, Characterisation and Reactions of Truly Cationic Ni<sup>I</sup>- Phosphine Complexes.
- Authors
Schwa, Miriam Mareen; Himmel, Daniel; Kacprzak, Sylwia; Radtke, Valentin; Kratzert, Daniel; Weis, Philippe; Wernet, Melanie; Peter, Andreas; Yassine, Zeinab; Schmitz, Dominik; Scheidt, Ernst-Wilhelm; Scherer, Wolfgang; Weber, Stefan; Feuerstein, Wolfram; Breher, Frank; Higelin, Alexander; Ingo Krossing
- Abstract
The recently published purely metallo-organic NiI salt [Ni(cod)2][Al(ORF)4] (1, cod=1,5-cyclooctadiene, RF= C(CF3)3) provides a starting point for a new synthesis strategy leading to NiI phosphine complexes, replacing cod ligands by phosphines. Clearly visible colour changes indicate reactions within minutes, while quantum chemical calculations (PBE0-D3(BJ)/def2-TZVPP) approve exergonic reaction enthalpies in all performed ligand exchange reactions. Hence, [Ni(dppp)2][Al(ORF)4] (2, dppp=1,3-bis(diphenylphosphino) propane), [Ni(dppe)2][Al(ORF)4] (3, dppe=1,3-bis(diphenyl- phosphino)ethane), three-coordinate [Ni(PPh3)3] [Al(ORF)4] (4) and a remarkable two-coordinate NiI phosphine complex [Ni(PtBu3)2][Al(ORF)4] (5) were characterised by single crystal X-ray structure analysis. EPR studies were performed, confirming a nickel d9 -configuration in complexes 2, 4 and 5. This result is supported by additional magnetization measurements of 4 and 5. Further investigations by cyclic voltammetry indicate relatively high oxidation potentials for these NiI compounds between 0.7 and 1.7 V versus Fc/Fc+. Screening reactions with O2 and CO gave first insights on the reaction behaviour of the NiI phosphine complexes towards small molecules with formation of mixed phosphine- CO-NiI complexes and oxidation processes yielding new NiI and/or NiII derivatives. Moreover, 4 reacted with CH2Cl2 at RT to give a dimeric NiII ylide complex (4c). As CH2Cl2 is a rather stable alkyl halide with relatively high C@Cl bond energies, 4 appears to be a suitable reagent for more general C@Cl bond activation reactions.
- Subjects
COMPLEX compounds synthesis; METAL complexes; PHOSPHINE; NICKEL compounds; CYCLOOCTADIENE; QUANTUM chemistry
- Publication
Chemistry - A European Journal, 2018, Vol 24, Issue 4, p918
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201704436