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These complexes were generated by Si-H bond activation with the release of H2 and the formation of N-Si and Ru-Si bonds. When the reaction of 1 was carried out in the presence of PhSiH3, the reaction only produced the analogous complexes [PPh3κ2-S,Si-(NSiPhH)(S2C7H4)Ruκ3-H,S,S'-H2B(C7H4NS2)2] (5a',b'. Density functional theory (DFT) calculations have been used to probe the bonding modes of boranes/silane with the ruthenium center.The influence of N-substituent and pKa of azole rings has been investigated for the performance of high-temp