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. 2015 Dec 1;54(49):14706-9.
doi: 10.1002/anie.201506475. Epub 2015 Oct 13.

[Ni(cod)2][Al(OR(F))4], a Source for Naked Nickel(I) Chemistry

Miriam M Schwab  1 , Daniel Himmel  1 , Sylwia Kacprzak  2 , Daniel Kratzert  1 , Valentin Radtke  1 , Philippe Weis  1 , Kallol Ray  3 , Ernst-Wilhelm Scheidt  4 , Wolfgang Scherer  4 , Bas de Bruin  5 , Stefan Weber  2   6 , Ingo Krossing  7
Affiliations

[Ni(cod)2][Al(OR(F))4], a Source for Naked Nickel(I) Chemistry

Miriam M Schwab et al. Angew Chem Int Ed Engl. .

Abstract

The straightforward synthesis of the cationic, purely organometallic Ni(I) salt [Ni(cod)2](+)[Al(OR(F))4](-) was realized through a reaction between [Ni(cod)2] and Ag[Al(OR(F))4] (cod = 1,5-cyclooctadiene). Crystal-structure analysis and EPR, XANES, and cyclic voltammetry studies confirmed the presence of a homoleptic Ni(I) olefin complex. Weak interactions between the metal center, the ligands, and the anion provide a good starting material for further cationic Ni(I) complexes.

Keywords: crystallography; cyclic voltammetry; density functional calculations; electron paramagnetic resonance; nickel(I) complexes.

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Figures

Figure 1
Figure 1
a) Molecular structure of 1. Thermal ellipsoids are shown at the 50% probability level. b) Cationic parts of the molecular structures of [Rh(cod)2]+[Al(ORF)4]− (3), [Ni(cod)2]+[Al(ORF)4]− (1) and [Ag(cod)2]+[Al(ORF)4]− (2) at 100 K. Thermal ellipsoids are drawn at the 50% probability level. Selected bond lengths (avg.) [pm] and torsion angles θ [°] (see procedure below): 3: dRh-C = 224.1, dC=C = 136.8, θ = 10.0; 1: dNi-C = 222.3,dC=C = 135.3, θ = 53.6;2: dAg-C = 248.7, dC=C = 134.5, θ = 88.5.
Figure 2
Figure 2
a) Continuous-wave EPR spectrum of a frozen solution of 1 in CH2Cl2 with ionic liquid additive to facilitate glass formation ([MeN(Octyl)3]+[Al(ORF)4]−, 0.1 M) at X-band (9.400 GHz) at 100 K (solid line). Simulated spectra using parameters given in the main text (dashed line). Parts of the spectra are magnified as indicated. Experimental conditions: microwave power, 1.99 mW; magnetic field modulation amplitude, 0.1 mT (100 kHz modulation frequency); time-constant, 81.92 ms. Inset: Optimized structure (PBE0/def2-TZVPP) of [Ni(cod)2]+ is shown with spin density contour plotted with a 0.003 a.u. cut-off. b) XANES spectra of a powdered sample of 1 diluted with boron nitride at 19 K (red) and 298 K (blue). In the inset is shown the corresponding first-derivative spectra (smoothed by moving average).
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