The η² Complex of Nickel Bis(diphenylphosphanyl)propane with Fullerene: {Ni(dppp)(η²‐C₆₀)}·(Solvent) Obtained by Reduction

Abstract

The η2 complex of nickel bis(diphenylphosphanyl)propane with fullerene, {Ni(dppp)(η2‐C60)}·(C6H14)0.84·(C6H4Cl2)0.16 (1) (C6H14: hexane, C6H4Cl2: o‐dichlorobenzene), has been obtained by reduction of the Ni(dppp)Cl2 and C60 mixture with sodium fluorenone in o‐dichlorobenzene and slow precipitation of the single crystals by diffusion of hexane. Nickel coordinates to the 6–6 bond of C60 by η2‐coordination to form Ni–C(C60) bonds with a length of 1.948–1.951(2) Å, which are the shortest M–C bonds among known η2 complexes of fullerenes. The 6–6 bond length [1.488(3) Å] where the Ni atom is coordinated is noticeably longer than the average length of other 6–6 bonds in C60 [1.388(2) Å]. Coordination of nickel to C60 results in the splitting of two bands for two IR‐active modes of C60 into three bands, because of the lower symmetry of C60, and a noticeable shift in the F1u(4) mode of C60 to lower frequencies, as a result of π back‐donation. The dark green complex manifests two absorption bands at 664 and 890 nm in the visible range. The complex is EPR silent since only a weak narrow signal with g = 2.0000 and ΔH = 0.17 mT was found in the EPR spectrum of 1 at room temperature, which originates from about 0.1 % of spins of the total amount of C60.

Tetrabutylammonium Salts of Aluminum(III) and Gallium(III) Phthalocyanine Radical Anions Bonded with Fluoren‐9‐olato− Anions and Indium(III) Phthalocyanine Bromide Radical Anions

“…Tetrabutylammonium bromide (Bu 4 N + )(Br − ) of 99 % purity was purchased from TCI. Sodium fluorenone ketyl was obtained as previously described . All manipulations for the syntheses of 1 – 3 were performed in a MBraun 150B‐G glove box with a controlled atmosphere and the contents of H 2 O and O 2 less than 1 ppm.…”

Layered Salts with Iron Hexadecachlorophthalocyanine Anions – The Formation of [{FeCl16Pc}2]3– Dimers Containing [FeICl16Pc(2–)]– and Diamagnetic [Fe0Cl16Pc(2–)]2–

“…Materials: Fe II Cl 16 Pc (80 %), PPNCl (97 %), and TBABr (99 %) were purchased from Aldrich. Sodium fluorenone ketyl was prepared as described elsewhere 32. All manipulations for the syntheses of 1 and 2 were carried out in a MBraun 150B‐G glove box with a controlled atmosphere, and the content of H 2 O and O 2 was less than 1 ppm.…”

The Salts of Copper Octafluoro- and Hexadecafluorophthalocyanines Containing [CuII(F8Pc)4–]2– Dianions and [CuF16Pc]− Monoanions

“…The reductant, sodium fluorenone ketyl, was obtained as described. 22 Solvents were purified under an argon atmosphere. The odichlorobenzene (C6H4Cl2) was distilled over CaH2 under reduced pressure, benzonitrile (C6H5CN) was distilled over sodium under reduced pressure and n-hexane was distilled over Na/benzophenone.…”