Cooperative B-H bond activation: dual site borane activation by redox active κ²-N,S-chelated complexes

Cooperative dual site activation of boranes by redox-active 1,3-N,S-chelated ruthenium species, mer-[PR₃{κ²-N,S-(L)}₂Ru{κ¹-S-(L)}], (mer-2a: R = Cy, mer-2b: R = Ph; L = NC₇H₄S₂), generated from the aerial oxidation of borate complexes, [PR₃{κ²-N,S-(L)}Ru{κ³-H,S,S'-BH₂(L)₂}] (trans-mer-1a: R = Cy, trans-mer-1b: R = Ph; L = NC₇H₄S₂), has been investigated. Utilizing the rich electronic behaviour of these 1,3-N,S-chelated ruthenium species, we have established that a combination of redox-active ligands and metal-ligand cooperativity has a big influence on the multisite borane activation. For example, treatment of mer-2a-b with BH₃·THF led to the isolation of fac-[PR₃Ru{κ³-H,S,S'-(NH₂BSBH₂N)(S₂C₇H₄)₂}] (fac-3a: R = Cy and fac-3b: R = Ph) that captured boranes at both sites of the κ²-N,S-chelated ruthenacycles. The core structure of fac-3a and fac-3b consists of two five-membered ruthenacycles [RuBNCS] which are fused by one butterfly moiety [RuB₂S]. Analogous fac-3c, [PPh₃Ru{κ³-H,S,S'-(NH₂BSBH₂N)(SC₅H₄)₂}], can also be synthesized from the reaction of BH₃·THF with [PPh₃{κ²-N,S-(SNC₅H₄)}{κ³-H,S,S'-BH₂(SNH₄C₅)₂}Ru], cis-fac-1c. In stark contrast, when mer-2b was treated with BH₂Mes (Mes = 2,4,6-trimethyl phenyl) it led to the formation of trans- and cis-bis(dihydroborate) complexes [{κ³-S,H,H-(NH₂BMes)Ru(S₂C₇H₄)}₂], (trans-4 and cis-4). Both the complexes have two five-membered [Ru-(H)₂-B-NCS] ruthenacycles with κ²-H-H coordination modes. Density functional theory (DFT) calculations suggest that the activation of boranes across the dual Ru-N site is more facile than the Ru-S one.