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Issue 43, 2017
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Cluster transformation of [Cu33-H)(μ3-BH4)((PPh2)2NH)3](BF4) to [Cu33-H)(μ21-S2CH)((PPh2)2NH)3](BF4) via reaction with CS2. X-ray structural characterisation and reactivity of cationic clusters explored by multistage mass spectrometry and computational studies

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Abstract

The copper nanocluster [Cu33-H)(μ3-BH4)LPh3](BF4), 1a·BF4 (LPh = (PPh2)2NH = dppa), can potentially react with substrates at either the coordinated hydride or borohydride sites. Reaction of 1a·BF4 with CS2 has given rise to [Cu33-H)(μ21-S2CH)LPh3](BF4), (2a·BF4), which was structurally characterised using electrospray ionisation (ESI) with high-resolution mass spectrometry (HRMS), X-ray crystallography, NMR, IR and UV-Vis spectroscopy. The copper(I) atoms adopt a planar trinuclear Cu3 geometry coordinated on the bottom face by a μ3-hydride, on the top face by a μ21-dithioformate and surrounded by three bridging LPh ligands. Reaction of 1a·BF4 with elemental sulfur gives the known cluster [Cu4(LPh-H + 2S)3](BF4), (3·BF4), which was structurally characterised via X-ray crystallography. ESI-MS of 2a·BF4 produces [Cu3(H)(S2CH)LPh3]+ and its gas-phase ion chemistry was examined under multistage mass spectrometry conditions using collision-induced dissociation (CID). The primary product, [Cu3(H)(S2CH)LPh2]+, formed via ligand loss, undergoes further fragmentation via loss of thioformaldehyde to give [Cu3(S)LPh2]+. DFT calculations exploring rearrangement and fragmentation of the model system [Cu3(H)(S2CH)LMe2]+ (LMe = (PMe2)2NH = dmpa) provide a feasible mechanism. Thus, coupling of the coordinated hydride with the dithioformate ligands gives [Cu3(S2CH2)LMe2]+, which then undergoes CH2S extrusion via C–S bond cleavage to give [Cu3(S)LMe2]+.

Graphical abstract: Cluster transformation of [Cu3(μ3-H)(μ3-BH4)((PPh2)2NH)3](BF4) to [Cu3(μ3-H)(μ2,μ1-S2CH)((PPh2)2NH)3](BF4) via reaction with CS2. X-ray structural characterisation and reactivity of cationic clusters explored by multistage mass spectrometry and computational studies

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Publication details

The article was received on 19 Sep 2017, accepted on 10 Oct 2017 and first published on 20 Oct 2017


Article type: Paper
DOI: 10.1039/C7DT03510A
Dalton Trans., 2017,46, 14995-15003

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    Cluster transformation of [Cu33-H)(μ3-BH4)((PPh2)2NH)3](BF4) to [Cu33-H)(μ21-S2CH)((PPh2)2NH)3](BF4) via reaction with CS2. X-ray structural characterisation and reactivity of cationic clusters explored by multistage mass spectrometry and computational studies

    H. Z. Ma, J. Li, A. J. Canty and R. A. J. O'Hair, Dalton Trans., 2017, 46, 14995
    DOI: 10.1039/C7DT03510A

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