Issue 20, 2015

Anionic coordination complexes of C60 and C70 with cyclopentadienyl and pentamethylcyclopentadienyl molybdenum dicarbonyl

Abstract

Crystalline anionic coordination complexes (PPN+){CpMo(CO)22-C60)} (1), (PPN+){CpMo(CO)22-C70)}·0.5C6H14 (2) and (PPN+){Cp*Mo(CO)22-C60)}·C6H5CN·C6H4Cl2 (3) containing cyclopentadienyl (1, 2) and pentamethylcyclopentadienyl (3) molybdenum dicarbonyl η2-coordinated to fullerenes have been obtained by the reaction of the (PPN+)(fullerene˙) salt with the {Cp(*)Mo(CO)3(2)}2 dimers (PPN+ is bis(triphenylphosphoranylidene)ammonium cation). The {CpMo(CO)22-C60(70))} anions contain neutral C60 and C70. The optical properties and geometry of the CpMo(CO)2 moieties in 1 and 2 are similar to those in (PPN+){CpMo0(CO)3}. The analysis of optical data for 3 shows that η2-coordinated C60 molecules are more negatively charged in 3 than in 1 and 2. Complexes 1–3 show weak EPR signals indicating that the major part of the samples is EPR silent and diamagnetic. Diamagnetism of the anions in 1–3 is explained by the chemical bond formation between the initially paramagnetic CpMoI(CO)2 and (fullerene)˙ units. The DFT calculations for 1 and 3 support the diamagnetic singlet ground state for both complexes, in which the singlet–triplet energy gaps calculated at the M11/cc-pVTZ-PP/cc-pVDZ level of theory are about 1.27 and 0.95 eV, respectively. According to the calculations, C60 molecules are more negatively charged in 3 than in 1 and that can be explained by stronger back donation from the molybdenum moieties to fullerenes.

Graphical abstract: Anionic coordination complexes of C60 and C70 with cyclopentadienyl and pentamethylcyclopentadienyl molybdenum dicarbonyl

Supplementary files

Article information

Article type
Paper
Submitted
11 Mar 2015
Accepted
14 Apr 2015
First published
17 Apr 2015

Dalton Trans., 2015,44, 9672-9681

Author version available

Anionic coordination complexes of C60 and C70 with cyclopentadienyl and pentamethylcyclopentadienyl molybdenum dicarbonyl

D. V. Konarev, A. V. Kuzmin, S. I. Troyanov, Y. Nakano, S. S. Khasanov, A. Otsuka, H. Yamochi, G. Saito and R. N. Lyubovskaya, Dalton Trans., 2015, 44, 9672 DOI: 10.1039/C5DT00970G

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