Synthesis and X-ray structures of hydridotris(1-pyrazolyl)borate carbonyl complexes of ruthenium

A series of new hydridotris(1-pyrazolyl)borate (Tp) carbonyl complexes of ruthenium were synthesized. Treatment of [TpRu(CO)2X] (X=Br, I) with Me3NO in MeCN afforded [TpRu(CO)(NCMe)X] (X=Br (1), I (2)). The reactions of 1 and 2 with either neutral isocyanides or anionic dialkyldithiocarbamates to produce [TpRu(CO)(CNR)X] (X=Br, R=PhCH2 (3); X=Br, R=tBu (4); X=I, R=PhCH2 (5) X=I, R=tBu (6)) and [TpRu(CO)(η2-S2CNR2)] (R=Me (7), Et (8)), respectively. Compounds 1 and 2 reacts with RSH–Et3N in THF or 1,2-dimethoxyethane at reflux to give mono- and dithiolato diruthenium products, (cis)-[Tp2Ru2(CO)2(μ-X)(μ-SR)] (X=I, R=iPr (11); X=Br, R=tBu (13); X=I, R=tBu (14)), (trans, anti-1)-[Tp2Ru2(CO)2(μ-SiPr)2] (9), (cis, syn)-[Tp2Ru2(CO)2(μ-SiPr)2] (10), (trans, anti-1)-[Tp2Ru2(CO)2(μ-StBu)2] (12), and (cis, anti-2)-[Tp2Ru2(CO)2(μ-SiPr)(μ-StBu)] (15). Compound 11 reacts with Me3NO to form stereo- and chemospecifically the first diruthenium sulfenate, (cis)-[Tp2Ru2(CO)2(μ-I)(μ-S(O)iPr)] (16) with the SO bond at the endo position with respect to carbonyls. Structures 8, 9, 10, 12, 14, 15, and 16 are described.