Synthesis, Structure and Gas‐Phase Reactivity of a Silver Hydride Complex [Ag 3 {(PPh 2 ) 2 CH 2 } 3 (μ 3 ‐H)(μ 3 ‐Cl)]BF 4

Mass spectrometry shows the way! MS analysis of silver salts treated with sodium borohydride in the presence of a bis(phosphino) ligand revealed the formation of novel silver hydride nanocluster cations instead of all silver nanocluster cations. This serendipitous discovery prompted the condensed-phase synthesis, isolation, and characterization of [Ag3{(Ph2P)2CH2}3(μ3-H)(μ3-Cl)]BF4⋅0.5 CHCl3.