Cooperative B–H and Si–H Bond Activations by κ 2 - N , S -Chelated Ruthenium Borate Complexes - Archive ouverte HAL Access content directly
Journal Articles Inorganic Chemistry Year : 2021

Cooperative B–H and Si–H Bond Activations by κ 2 - N , S -Chelated Ruthenium Borate Complexes

Abstract

Cooperative E–H (E = B, Si) bond activations employing κ2-N,S-chelated ruthenium borate species, [PPh3{κ2-N,S-(NS2C7H4)}Ru{κ3-H,S,S′-H2B(NC7H4S2)2}], (1) are established. Treatment of 1 with BH3·SMe2 yielded the six-membered ruthenaheterocycle [PPh3{κ2-S,H-(BH3NS2C7H4)}Ru{κ3-H,S,S’-H2B(C7H4NS2)2}] (2) formed by a hemilabile ring opening of a Ru–N bond and capturing of a BH3 unit coordinated in an “end-on” fashion. On the other hand, the bulky borane H2BMes shows different reactivity with 1 that led to the formation of the two dihydroborate complexes [{κ3-S,H,H-(NBH2Mes)(S2C7H4)}Ru{κ3-H,S,S’-H2B(C7H4NS2)2}] (3) and [PPh3{κ3-S,H,H-(NBH2Mes)(S2C7H4)}Ru(κ2-N,S-C7H4NS2)] (4), in which H2BMes has been inserted into the Ru–N bond of the initial κ2-N,S-chelated ligand. In an attempt to directly activate hydrosilanes by 1, reactions were carried out with H2SiPh2 that yielded two isomeric five-membered ruthenium silyl complexes, namely [PPh3{κ2-S,Si-(NSiPh2)(S2C7H4)}Ru{κ3-H,S,S’-H2B(C7H4NS2)2}] (5a,b), and the hydridotrisilyl complex [Ru(H){κ2-S,Si-(SiPh2NC7H4S2}3] (6). 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 [PPh3{κ2-S,Si-(NSiPhH)(S2C7H4)}Ru{κ3-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.
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Dates and versions

hal-03150014 , version 1 (23-02-2021)

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Mohammad Zafar, Rongala Ramalakshmi, Asif Ahmad, P. Antharjanam, Sébastien Bontemps, et al.. Cooperative B–H and Si–H Bond Activations by κ 2 - N , S -Chelated Ruthenium Borate Complexes. Inorganic Chemistry, 2021, 60 (2), pp.1183-1194. ⟨10.1021/acs.inorgchem.0c03306⟩. ⟨hal-03150014⟩
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