University of Oulu

Minna M. Karjalainen, Torben Wiegand, J. Mikko Rautiainen, Andreas Wagner, Helmar Görls, Wolfgang Weigand, Raija Oilunkaniemi, Risto S. Laitinen, Competitive Te-Te and C-Te bond cleavage in the oxidative addition of diaryl and dialkyl ditellurides to Pt(0) centers, Journal of Organometallic Chemistry, Volumes 836–837, 2017, Pages 17-25, ISSN 0022-328X, https://doi.org/10.1016/j.jorganchem.2017.03.004

Competitive Te-Te and C-Te bond cleavage in the oxidative addition of diaryl and dialkyl ditellurides to Pt(0) centers

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Author: Karjalainen, Minna M.1; Wiegand, Torben2; Rautiainen, J. Mikko1,3;
Organizations: 1Laboratory of Inorganic Chemistry, Environmental and Chemical Engineering, University of Oulu, P. O. Box 3000, FI-90014, Oulu, Finland
2nstitut für Anorganische und Analytische Chemie, Humboldt-Str. 8, 07743, Friedrich-Schiller-Universität Jena, Germany
3Present address: Department of Chemistry, University of Jyväskylä, P.O. Box 35, FI-40014, Jyväskylä, Finland
4Institut für Anorganische und Analytische Chemie, Humboldt-Str. 8, 07743, Friedrich-Schiller-Universität Jena, Germany
Format: article
Version: accepted version
Access: open
Online Access: PDF Full Text (PDF, 2.2 MB)
Persistent link: http://urn.fi/urn:nbn:fi-fe202001202747
Language: English
Published: Elsevier, 2017
Publish Date: 2020-01-20
Description:

Abstract

The oxidative addition reaction of ditellurides R₂Te₂ [R = ⁿBu, Ph, Th (2-thienyl, C4H3S)] to [Pt(η²-nb)(dppn)] (nb = norbornene, dppn = 1,2-bis(diphenylphosphano)naphthalene) was found to afford [Pt(TeR)₂(dppn)] [R = ⁿBu (1), Ph (2), Th (3)] and [Pt(TeR)(R)(dppn)] [R = Ph (4), Th (5)] as a result of the cleavage of the Te-Te or C-Te bond, respectively. The reactions and the product distributions were monitored by 31P{1H} NMR spectroscopy. The spectral interpretation was assisted by the high-yield preparation of [Pt(TePh)₂(dppn)] (2) and [Pt(TeTh)₂(dppn)] (3) by ligand exchange reactions from [PtCl₂(dppn)], and by the crystal structure determinations and spectral characterizations of 2 and 3. Two series of reactions were carried out both at room temperature and at −80 °C. One involved the addition of the toluene solution of R₂Te₂ to that of [Pt(η²-nb)(dppn)], and the other the addition of [Pt(η²-nb)(dppn)] solution to the R₂Te₂ solution. The oxidative addition of ⁿBu₂Te₂ to [Pt(η²-nb)(dppn)] yielded solely [Pt(TenBu)₂(dppn)]. In case of Ph₂Te₂ and Th₂Te₂, the reaction of equimolar amounts of ditelluride and [Pt(η²-nb)(dppn)] afforded only [Pt(TeR)(R)(dppn)] (R = Ph, Th), but when an excess of R₂Te₂ was used, the addition of [Pt(η²-nb)(dppn)] to the ditelluride resulted in the formation of a mixture of [Pt(TeR)₂(dppn)] and [Pt(TeR)(R)(dppn)] with the latter the main component. An excess of R₂Te₂ and the lowering of the temperature favoured the formation of [Pt(TeR)₂(dppn)]. The reaction energetics in toluene was calculated at revPBE/def2-TZVP(-f) level of theory. The increase of the electron withdrawing nature of the organic substituent rendered [Pt(TeR)(R)(dppn)] increasingly stable with respect to [Pt(TeR)₂(dppn)]. The computation of the energy profiles of the likely pathways of the oxidative addition indicated that concurrent formation of [Pt(TeR)₂(dppn)] and [Pt(TeR)(R)(dppn)] (R = Ph, Th) may be more likely than the formation of the latter due to the decomposition of the former. This was verified experimentally by stirring pure [Pt(TeR)₂(dppn)] in toluene for a prolonged time at room temperature. No decomposition was observed.

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Series: Journal of organometallic chemistry
ISSN: 0022-328X
ISSN-E: 1872-8561
ISSN-L: 0022-328X
Volume: 836–837
Pages: 17 - 25
DOI: 10.1016/j.jorganchem.2017.03.004
OADOI: https://oadoi.org/10.1016/j.jorganchem.2017.03.004
Type of Publication: A1 Journal article – refereed
Field of Science: 116 Chemical sciences
Subjects:
Funding: Financial support from Emil Aaltonen Foundation (M. M. K.) and Inorganic Materials Graduate Program (M. M. K.) are gratefully acknowledged.
Copyright information: © 2017 Elsevier B.V. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/.
  https://creativecommons.org/licenses/by-nc-nd/4.0/