Synthesis, Structural Characterization, and Gas-Phase Unimolecular Reactivity of the Silver Hydride Nanocluster [Ag₃((PPh₂)₂CH₂)₃(μ₃-H)](BF₄)₂

Abstract

A bis(diphenylphosphino)methane-ligated trinuclear silver hydride nanocluster, [Ag3((Ph2P)2CH2)3(μ3-H)](BF4)2, featuring three silver(I) ions coordinated to a μ3-hydride, and its deuteride analogue, [Ag3((Ph2P)2CH2)3(μ3-D)](BF4)2, have been isolated and structurally characterized using electrospray ionization mass spectrometry (ESI-MS), X-ray crystallography, NMR and IR spectroscopy. The position of the deuteride in [Ag3((Ph2P)2CH2)3(μ3-D)](BF4)2 was determined by neutron diffraction. ESI-MS of [Ag3L3(μ3-H/D)](BF4)2 [L = ((Ph2P)2CH2)2] produces [Ag3L3(μ3-H/D)](2+) and [Ag3L3(μ3-H/D)(BF4)](+). A rich gas-phase ion chemistry of [Ag3L3(μ3-H/D)](2+) is observed under conditions of collision-induced dissociation (CID) and electron-capture dissociation (ECD). CID gives rise to the following complementary ion pairs: [Ag3L2](+) and [L+(H/D)](+); [Ag2(H/D)L2](+) and [AgL](+); [Ag2(H/D)L](+) and [AgL2](+). ECD gives rise to a number of dissociation channels including loss of the bis(phosphine) ligand, fragmentation of a coordinated bis(phosphine) ligand via C-P bond activation, and loss of a hydrogen (deuterium) atom with concomitant formation of [Ag3L3](+). Under CID conditions, [Ag3L3(μ3-H/D)(BF4)](+) fragments via ligand loss, the combined loss of a ligand and [H,B,F4], and cluster fragmentation to give [Ag2(BF4)L2](+) and [Ag2(L-H)L](+) [where (L-H) = (Ph2P)2CH(-)].

Bis(dimethylphosphino)methane-ligated silver chloride, cyanide and hydride cluster cations: Synthesis and gas-phase unimolecular reactivity

“…(33)) ( Fig. 5a) similar to what was previously observed [6]. DFT calculations suggest that the loss of AgCN should be favoured, as this pathway is less endothermic.…”

“…Previous ESI/MS studies of the mixture formed upon reaction of silver salts with sodium borohydride in the presence of bis-(diphenylphosphino)methane (dppm) revealed the formation of the following silver hydride cluster cations: [Ag 3 H(dppm) 3 ] 2+ , [Ag 3 HCl(dppm) 3 ] + and [Ag 10 H 8 (dppm) 6 ] 2+ [3r,6]. This prompted the mass spectrometry directed synthesis and structural characterization of the clusters [Ag 3 HCl(dppm) 3 ]BF 4 , [Ag 3 Cl 2 (dppm) 3 ]BF 4 and [Ag 3 H(dppm) 3 ](BF 4 ) 2 .…”

Synthesis, structure and gas-phase reactivity of the mixed silver hydride borohydride nanocluster [Ag3(μ3-H)(μ3-BH4)LPh3]BF4(LPh= bis(diphenylphosphino)methane)

“…(2e,2c) bonds, the structure and bonding of this cluster was analysed based on simple electron counting rules. [33][34][35][36][37] As expected, a transition metal centre with a d 10 Å), where the corresponding anti-bonding skeletal molecular orbitals are also fully occupied. 38 With regards to the unimolecular fragmentation chemistry, the calculations indicate that the first loss of the ligand, L (eqn (12)), from [Ag 3 (H)(BH 4 )L Me 3 ] + results in transferring the hydride to Ag 2 and causes this centre to adopt a mainly linear structure with a very weak interaction with Ag 1 (Fig.…”

“…39 In general, the HOMO of d 10 complexes (ML n ) with a coordination number greater than two (n > 2) suffers from a slight anti-bonding interaction between L and M, leading to weakening of the M-L bonds. However, this anti-bonding interaction disappears in linear d 10…”

Synthesis, Characterization, and Reactivity of the Group 11 Hydrido Clusters [Ag6H4(dppm)4(OAc)2] and [Cu3H(dppm)3(OAc)2]

“…Consequently, Ag I -H complexes have proven to be relatively rare. 21,[23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38] Moreover, the examples isolated thus far are either homometallic monohydrides, e.g., [ 10 ] 2+ ). 39 Herein, we report the synthesis and characterization of the first structurally characterized homometallic silver polyhydrido cluster, [Ag 6 H 4 (dppm) 4 (OAc) 2 ].…”