Protonation of metal–metal bonds in nitrosyl-bridged diruthenium complexes

The addition reaction of a proton towards the nitrosyl-bridged diruthenium complexes [Ru2(CO)4(μ-NO)(μ-PtBu2)(μ-P^P)] (P^P = Me2PCH2PMe2, dmpm, 1b; P^P = Ph2PC(=CH2)PPh2, dppen, 1c; P^P = Ph2PN(H)PPh2, dppa, 1d) has been investigated. The species 1b–d exhibit an enhanced metal basicity and react spontaneously with a proton (from HBF4) in diethyl ether to afford the corresponding oxidative addition products [Ru2(CO)4(μ-NO)(μ-H)(μ-PtBu2)(μ-P^P)]BF4 (2b–d) in good yields. The molecular structures of 2b–d were confirmed by X-ray diffraction studies revealing a shortening of the metal–metal bond upon protonation in each case.

Graphical abstractProtonation reactions of the metal–metal bond in nitrosyl-bridged diruthenium complexes were described. During the oxidative addition of a hydrido ligand towards the compounds [Ru2(CO)4(μ-NO)(μ-PtBu2)(μ-P^P)] (P^P = Me2PCH2PMe2, 1b; P^P = Ph2PC(=CH2)PPh2, 1c; P^P = Ph2PN(H)PPh2, 1d) the metal–metal bonds were significantly shortened.Figure optionsDownload full-size imageDownload as PowerPoint slide