Trifluorophosphine hydrides

Table 1. Trifluorophosphine-Hydride Complexes Prepared from Transition-Metal Salts...

In some cases H2 can interact directly with binary metal-trifluorophosphine complexes under mild conditions with or without addition of PF3 or UV irradiation (method B), and group IV hydrides have also been utilized (method C). 

Thus when the >73-l,l-dimethylallyltris(trifluorophosphine) complexes of cobalt or rhodium are gently warmed a rearrangement to the 73-l,2-isomer occurs (56, 295). The postulated mechanism involves a diene-metal hydride intermediate (Scheme 9). The small PF3 ligand can also be added directly to coordinatively unsaturated 3-allylic systems or to chloro-bridged structures (method H). 

Alternatively, treatment of trifluorophosphine metallates with R3MC1 (method B) or via metal-metal bond cleavage reactions of dinuclear PF3 metal complexes with a group IV metal hydride R3MH (method C) have been useful synthetic methods, e.g.,... 

Reductive fluorophosphination of metal halides in the presence of hydrogen will lead to some very stable complexes which contain covalently bound hydrogen (8.187) and (8.188). The proton can be removed from trifluorophosphine metal hydrides by weak bases, to form ionic trifluorophosphine metallates such as K Ir(PF3) . ... 

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