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


ABSTRACT: Cooperative dual site activation of boranes by redox-active 1,3-N,S-chelated ruthenium species, mer-[PR32-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, [PR32-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 [PPh32-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.

SUBMITTER: Zafar M 

PROVIDER: S-EPMC9337726 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

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Cooperative B-H bond activation: dual site borane activation by redox active κ<sup>2</sup>-<i>N</i>,<i>S</i>-chelated complexes.

Zafar Mohammad M   Ahmad Asif A   Saha Suvam S   Ramalakshmi Rongala R   Roisnel Thierry T   Ghosh Sundargopal S  

Chemical science 20220623 29


Cooperative dual site activation of boranes by redox-active 1,3-<i>N</i>,<i>S</i>-chelated ruthenium species, <i>mer</i>-[PR<sub>3</sub>{κ<sup>2</sup>-<i>N</i>,<i>S</i>-(L)}<sub>2</sub>Ru{κ<sup>1</sup>-<i>S</i>-(L)}], (<i>mer</i>-2a: R = Cy, <i>mer</i>-2b: R = Ph; L = NC<sub>7</sub>H<sub>4</sub>S<sub>2</sub>), generated from the aerial oxidation of borate complexes, [PR<sub>3</sub>{κ<sup>2</sup>-<i>N</i>,<i>S</i>-(L)}Ru{κ<sup>3</sup>-<i>H</i>,<i>S</i>,<i>S</i>'-BH<sub>2</sub>(L)<sub>2</sub>}] (<  ...[more]

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