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. Issue 43 (20th October 2017)

• Record Type: Journal Article
• Authors: Ma, Howard Z.; Li, Jiaye; Canty, Allan J.; O'Hair, Richard A. J.
• Is Part Of: Dalton transactions. Volume 46:Issue 43(2017)
• Page Start: 14995
• Page End: 15003
• Publication Date: 2017-10-20
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c7dt03510a
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : [Cu3 (μ3 -H)(μ3 -BH4 )((PPh2 )2 NH)3 ](BF4 ) reacts with CS2 to produce [Cu3 (μ3 -H)(μ2, μ1 -S2 CH)((PPh2 )2 NH)3 ](BF4 ), whose cation loses CH2 S upon ligand loss. Abstract : The copper nanocluster [Cu3 (μ3 -H)(μ3 -BH4 )L Ph 3 ](BF4 ), 1a·BF4 (L Ph = (PPh2 )2 NH = dppa), can potentially react with substrates at either the coordinated hydride or borohydride sites. Reaction of1a·BF4 with CS2 has given rise to [Cu3 (μ3 -H)(μ2, μ1 -S2 CH)L Ph 3 ](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 μ2, μ1 -dithioformate and surrounded by three bridging L Ph ligands. Reaction of1a·BF4 with elemental sulfur gives the known cluster [Cu4 (L Ph -H + 2S)3 ](BF4 ), (3·BF4 ), which was structurally characterised via X-ray crystallography. ESI-MS of2a·BF4 produces [Cu3 (H)(S2 CH)L Ph 3 ] + and its gas-phase ion chemistry was examined under multistage mass spectrometry conditions using collision-induced dissociation (CID). The primary product, [Cu3 (H)(S2 CH)L Ph 2 ] +, formed via ligand loss, undergoes further fragmentation via loss of thioformaldehyde to give [Cu3 (S)L Ph 2 ] + . DFT calculations exploring rearrangement and fragmentation of the model system [Cu3 (H)(S2 CH)L Me 2 ] + (L Me = (PMe2 )2 NH = dmpa) provide a feasible mechanism. Thus, coupling of the coordinated hydride with the dithioformate ligands gives [Cu3 (S2 CH2 )L Me 2 ] +, which then undergoes CH2 S extrusion via C–S bond cleavage to give [Cu3 (S)L Me 2 ] + .