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| Naji, M. |
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| Motta, Antonella |
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| Aletan, Dirar |
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| Mohamed, Tarek |
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| Ertürk, Emre |
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| Taccardi, Nicola |
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| Petrov, R. H. | Madrid |
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| Casati, R. |
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| Kalteremidou, Kalliopi-Artemi | Brussels |
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| Azam, Siraj |
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| Ospanova, Alyiya |
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| Ali, M. A. |
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| Popa, V. |
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| Rančić, M. |
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| Ollier, Nadège |
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| Azevedo, Nuno Monteiro |
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| Landes, Michael |
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Schmitz, Dominik
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article
Synthesis, Characterisation and Reactions of Truly Cationic Ni(I)–Phosphine Complexes
Abstract
<jats:title>Abstract</jats:title><jats:p>The recently published purely metallo‐organic Ni<jats:sup>I</jats:sup> salt [Ni(cod)<jats:sub>2</jats:sub>][Al(OR<jats:sup>F</jats:sup>)<jats:sub>4</jats:sub>] (<jats:bold>1</jats:bold>, cod=1,5‐cyclooctadiene, R<jats:sup>F</jats:sup>=C(CF<jats:sub>3</jats:sub>)<jats:sub>3</jats:sub>) provides a starting point for a new synthesis strategy leading to Ni<jats:sup>I</jats:sup> 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)<jats:sub>2</jats:sub>][Al(OR<jats:sup>F</jats:sup>)<jats:sub>4</jats:sub>] (<jats:bold>2</jats:bold>, dppp=1,3‐bis(diphenylphosphino)propane), [Ni(dppe)<jats:sub>2</jats:sub>][Al(OR<jats:sup>F</jats:sup>)<jats:sub>4</jats:sub>] (<jats:bold>3</jats:bold>, dppe=1,3‐bis(diphenyl‐phosphino)ethane), three‐coordinate [Ni(PPh<jats:sub>3</jats:sub>)<jats:sub>3</jats:sub>][Al(OR<jats:sup>F</jats:sup>)<jats:sub>4</jats:sub>] (<jats:bold>4</jats:bold>) and a remarkable two‐coordinate Ni<jats:sup>I</jats:sup> phosphine complex [Ni(P<jats:italic>t</jats:italic>Bu<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>][Al(OR<jats:sup>F</jats:sup>)<jats:sub>4</jats:sub>] (<jats:bold>5</jats:bold>) were characterised by single crystal X‐ray structure analysis. EPR studies were performed, confirming a nickel d<jats:sup>9</jats:sup>‐configuration in complexes <jats:bold>2</jats:bold>, <jats:bold>4</jats:bold> and <jats:bold>5</jats:bold>. This result is supported by additional magnetization measurements of <jats:bold>4</jats:bold> and <jats:bold>5</jats:bold>. Further investigations by cyclic voltammetry indicate relatively high oxidation potentials for these Ni<jats:sup>I</jats:sup> compounds between 0.7 and 1.7 V versus Fc/Fc<jats:sup>+</jats:sup>. Screening reactions with O<jats:sub>2</jats:sub> and CO gave first insights on the reaction behaviour of the Ni<jats:sup>I</jats:sup> phosphine complexes towards small molecules with formation of mixed phosphine‐CO‐Ni<jats:sup>I</jats:sup> complexes and oxidation processes yielding new Ni<jats:sup>I</jats:sup> and/or Ni<jats:sup>II</jats:sup> derivatives. Moreover, <jats:bold>4</jats:bold> reacted with CH<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub> at RT to give a dimeric Ni<jats:sup>II</jats:sup> ylide complex (<jats:bold>4 c</jats:bold>). As CH<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub> is a rather stable alkyl halide with relatively high C−Cl bond energies, <jats:bold>4</jats:bold> appears to be a suitable reagent for more general C−Cl bond activation reactions.</jats:p>