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DOI: 10.1039/D1SC90239C (Correction) Chem. Sci., 2021, 12, 15772-15774

Correction: HCOOH disproportionation to MeOH promoted by molybdenum PNP complexes

Elisabetta Alberico *ab, Thomas Leischner a, Henrik Junge *a, Anja Kammer a, Rui Sang a, Jenny Seifert a, Wolfgang Baumann a, Anke Spannenberg a, Kathrin Junge a and Matthias Beller *a
aLeibniz-Institut für Katalyse e. V., Albert-Einstein Straße 29a, 18059 Rostock, Germany. E-mail: henrik.junge@catalysis.de; matthias.beller@catalysis.de
bIstituto di Chimica Biomolecolare, Consiglio Nazionale delle Ricerche, tr. La Crucca 3, 07100 Sassari, Italy. E-mail: elisabetta.alberico@cnr.it

Received 9th November 2021 , Accepted 9th November 2021

First published on 23rd November 2021

Abstract

Correction for ‘HCOOH disproportionation to MeOH promoted by molybdenum PNP complexes’ by Elisabetta Alberico et al., Chem. Sci., 2021, 12, 13101–13119, DOI: 10.1039/D1SC04181A.

The authors regret that in Scheme 2 of the original article, complexes 7 and 8 were drawn incorrectly. The solid-state structure of both complexes, as established by X-ray analysis, had been previously reported (7 (ref. 1) and 8 (ref. 2)). In both complexes, the PNP ligand adopts a facial tridentate coordination to molybdenum and not a meridional one, as erroneously shown in Scheme 2 of the original article. The correct ligand arrangements in the metal coordination sphere for complexes 7 and 8 are reported below in Scheme 1.
image file: d1sc90239c-s1.tif
Scheme 1 Mo–PNP complexes tested in the dehydrogenation of HCOOH.

Please note that complex 8 is also shown in Scheme 4 in the proposed mechanism for HCOOH decarbonylation (green part), and in Fig. 2. In both cases, the correct structure for complex 8 is reported below in Scheme 2 and Fig. 1.


image file: d1sc90239c-s2.tif
Scheme 2 Proposed mechanisms for HCOOH dehydrogenation (red), disproportionation (blue) and decarbonylation (green) promoted by 5. Evidence for the formation of a Mo(IV) species is based on the detection by NMR of H2 and HD following addition of DCOOD to Mo(H)n species (see Fig. SI-31).

image file: d1sc90239c-f1.tif
Fig. 1 1H and 31P{1H} NMR spectra of a toluene-d8 solution of {Mo(CH3CN)(CO)2(HN[(CH2CH2P)(CH(CH3)2)2]2} 4 in the presence of 100 equivalents of HCOOH ([Mo] 10−2 M, [HCOOH] 1 M), before (a) and after heating at 90 °C for 1 hour (b). Spectra were recorded at room temperature. Signals related to complex 5 are marked by red dots.

Furthermore, a mistake was made in the caption of Fig. 6, showing the solid-state structure of complex 9: the latter has been incorrectly described as a Mo(I)-hydride species {Mo(H)(CO)2(CH3CN)[CH3N(CH2CH2P(CH(CH3)2)2)2]}. The correct formula, in agreement with the X-ray structure, is as follows and is shown above in Fig. 2: {Mo(CO)2(CH3CN)[CH3N(CH2CH2P(CH(CH3)2)2)2]}.


image file: d1sc90239c-f2.tif
Fig. 2 Molecular structure of {Mo(CO)2(CH3CN)[CH3N(CH2CH2P(CH(CH3)2)2)2]} 9. Displacement ellipsoids correspond to 30% probability. Hydrogen atoms are omitted for clarity.

The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.

Notes and references

  1. T. Leischner, A. Spannenberg, K. Junge and M. Beller, Synthesis of Molybdenum Pincer Complexes and Their Application in the Catalytic Hydrogenation of Nitriles, ChemCatChem, 2020, 12, 4543 CrossRef CAS.
  2. T. Leischner, A. Spannenberg, K. Junge and M. Beller, Molecular Defined Molybdenum–Pincer Complexes and Their Application in Catalytic Hydrogenations, Organometallics, 2018, 37, 4402 CrossRef CAS.
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