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Issue 32, 2016
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Synthesis of a labile sulfur-centred ligand, [S(H)C(PPh2S)2]: structural diversity in lithium(i), zinc(ii) and nickel(ii) complexes

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Abstract

A high-yield synthesis of [Li{S(H)C(PPh2S)2}]2 [Li2·(3)2] was developed and this reagent was used in metathesis with ZnCl2 and NiCl2 to produce homoleptic complexes 4 and 5b in 85 and 93% yields, respectively. The solid-state structure of the octahedral complex [Zn{S(H)C(PPh2S)2}2] (4) reveals notable inequivalence between the Zn–S(C) and Zn–S(P) contacts (2.274(1) Å vs. 2.842(1) and 2.884(1) Å, respectively). Two structural isomers of the homoleptic complex [Ni{S(H)C(PPh2S)2}2] were isolated after prolonged crystallization processes. The octahedral green Ni(II) isomer 5a exhibits the two monoprotonated ligands bonded in a tridentate (S,S′,S′′) mode to the Ni(II) centre with three distinctly different Ni–S bond lengths (2.3487(8), 2.4500(9) and 2.5953(10) Å). By contrast, in the red-brown square-planar complex 5b the two ligands are S,S′-chelated to Ni(II) (d(Ni–S) = 2.165(2) and 2.195(2) Å) with one pendant PPh2S group. DFT calculations revealed that the energetic difference between singlet and triplet state octahedral and square-planar isomers of the Ni(II) complex is essentially indistinguishable. Consistently, VT and 31P CP/MAS NMR spectroscopic investigations indicated that a mixture of isomers exists in solution at room temperature, while the singlet state square-planar isomer 5b becomes favoured at −40 °C.

Graphical abstract: Synthesis of a labile sulfur-centred ligand, [S(H)C(PPh2S)2]−: structural diversity in lithium(i), zinc(ii) and nickel(ii) complexes

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Supplementary files

Article information


Submitted
27 Jun 2016
Accepted
18 Jul 2016
First published
19 Jul 2016

Dalton Trans., 2016,45, 12691-12701
Article type
Paper

Synthesis of a labile sulfur-centred ligand, [S(H)C(PPh2S)2]: structural diversity in lithium(I), zinc(II) and nickel(II) complexes

R. Thirumoorthi, T. Chivers, S. Häggman, A. Mansikkamäki, I. S. Morgan, H. M. Tuononen, M. Lahtinen and J. Konu, Dalton Trans., 2016, 45, 12691
DOI: 10.1039/C6DT02565J

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