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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

Citation

Ma, HZ and Li, J and Canty, AJ and O'Hair, RAJ, 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, Dalton Transactions, 46 pp. 14995-15003. ISSN 1477-9226 (2017) [Refereed Article]


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DOI: doi:10.1039/c7dt03510a

Abstract

The copper nanocluster [Cu33-H)(μ3-BH4)LPh3](BF4), 1aBF4 (LPh = (PPh2)2NH = dppa), can potentially react with substrates at either the coordinated hydride or borohydride sites. Reaction of 1aBF4 with CS2 has given rise to [Cu33-H)(μ21-S2CH)LPh3](BF4), (2aBF4), 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 1aBF4 with elemental sulfur gives the known cluster [Cu4(LPh-H + 2S)3](BF4), (3BF4), which was structurally characterised via X-ray crystallography. ESI-MS of 2aBF4 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 CS bond cleavage to give [Cu3(S)LMe2]+.

Item Details

Item Type:Refereed Article
Keywords:copper cluster, DFT, mass spectrometry, computation
Research Division:Chemical Sciences
Research Group:Other Chemical Sciences
Research Field:Organometallic Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Canty, AJ (Professor Allan Canty)
ID Code:122272
Year Published:2017
Deposited By:Chemistry
Deposited On:2017-11-08
Last Modified:2017-11-08
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