Hydrides thiolato

In 2009, Rauchfuss and coworkers succeeded in the synthesis of the Fe- i-H-Ni complex [(CO)3Fe(pdt)(p-H)Ni(dppe)]BF4 28 (pdt = 1,3-propanedithiolate, dppe = 1,2-C2H4(PPh2)2) as a model for [NiFeJ-hydrogenases (Scheme 64) [212]. The structure of 28 was characterized by X-ray crystallographic analysis. This is the first example of an Fe-Ni thiolato hydride complex. Evolution of H2 by electrochemical reduction of CF3CO2H (pXa = 12.65) was observed in the presence of the catalytic amounts of 28. 

The alkylidyne complexes, L Mo(CR) (Lra = Tp(CO)2, (bpy)Br(CO)2 R, e.g., Ph derivatives), react with one equivalent of propylene sulfide to form thioacyl complexes, L Mo(r/2-SCR). In the case of Tp(CO)2Mo(r/2-SCCf,114Me-4) conversion into dithiocarboxylate, mixed thioselenocarboxylate/thio-latocarbene, cc-thiolatoalkyl, and a,a-bis(thiolato)alkyl species has been demonstrated 897 More recently, related thiocarboxamide and alkoxythiocarbonyl chemistry has been reported 898 Moreover, Mo(CO)L2 (L = depe, dppe) react with HC(S)NMe2 to produce thiocarboxamide hydrides (389) that convert at 125 °C to aminomethylidyne hydrosulfides (390).8"... 

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