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Oxidative addition of tetrathiocins to palladium(0) and platinum(0): a route to dithiolate coordination complexes

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Abstract

The preparation of a series of 4,4′,5,5′-substituted benzo-fused 1,2,5,6-tetrathiocins X2C6H2S4C6H2X2 (1a–1g) were prepared from the reaction of S2Cl2 with 1,2-C6H4X2 (X = OMe, OEt; X2 = OCH2O, OCH2CH2O, OCH2CH2CH2O, MeNC([double bond, length as m-dash]O)NMe, O(CH2CH2O)4). The oxidative addition of 1a–1g to zero-valent Pd2dba3 or Pt2dba3 (dba = dibenzylideneacetone) in the presence of bis (diphenylphosphino)ethane (dppe) resulted in formation of the substituted mononuclear benzenedithiolate complexes M(L)(dppe) [L = dithiolate ligand; 2a–2g (M = Pd) and 3a–3g (M = Pt)] in 37–89% yield based on recrystallized material. Representative examples of M(L)(dppf) [dppf = bis-diphenylphosphinoferrocene; 4a, 4g (M = Pd) and 5g (M = Pt)] were prepared in a similar fashion. The structures of all derivatives were determined by X-ray diffraction, multinuclear NMR and elemental analysis. The reactivity of the two crown ether dithiolate complexes, 2g and 4g, with 1 equivalent of NaBPh4 led to isolation of the 1 : 1 complexes in which the Na+ cation is bound in the macrocyclic crown, [Na(2g)(MeOH)2][BPh4] and [Na(4g)][BPh4] whose structures were determined by X-ray diffraction. Electrochemical studies supported through DFT calculations on the crown ether derivatives revealed a series of ligand-based oxidation waves corresponding to the dithiolate ligand (and dppf for 4g and 5g) whose redox potentials were shifted by ca. +0.1 V on binding to Na+.

Graphical abstract: Oxidative addition of tetrathiocins to palladium(0) and platinum(0): a route to dithiolate coordination complexes

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Supplementary files

Article information


Submitted
08 May 2020
Accepted
22 May 2020
First published
01 Jun 2020

Dalton Trans., 2020, Advance Article
Article type
Paper

Oxidative addition of tetrathiocins to palladium(0) and platinum(0): a route to dithiolate coordination complexes

L. K. Watanabe, J. D. Wrixon, Z. S. Ahmed, J. J. Hayward, P. Abbasi, M. Pilkington, C. L. B. Macdonald and J. M. Rawson, Dalton Trans., 2020, Advance Article , DOI: 10.1039/D0DT01678K

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