Cooperative B-H Bond Activation: Dual Site Borane Activation by Redox Active κ-,-chelated Complexes

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2022 Aug 17

PMID 35974760

Authors

Mohammad Zafar

Asif Ahmad

Suvam Saha

Rongala Ramalakshmi

Thierry Roisnel

Sundargopal Ghosh

Affiliations

Soon will be listed here.

Abstract

Cooperative dual site activation of boranes by redox-active 1,3-,-chelated ruthenium species, -[PR{κ-,-(L)}Ru{κ--(L)}], (-2a: R = Cy, -2b: R = Ph; L = NCHS), generated from the aerial oxidation of borate complexes, [PR{κ-,-(L)}Ru{κ-,,'-BH(L)}] (--1a: R = Cy, --1b: R = Ph; L = NCHS), has been investigated. Utilizing the rich electronic behaviour of these 1,3-,-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 -2a-b with BH·THF led to the isolation of -[PRRu{κ-,,'-(NHBSBHN)(SCH)}] (-3a: R = Cy and -3b: R = Ph) that captured boranes at both sites of the κ-,-chelated ruthenacycles. The core structure of -3a and -3b consists of two five-membered ruthenacycles [RuBNCS] which are fused by one butterfly moiety [RuBS]. Analogous -3c, [PPhRu{κ-,,'-(NHBSBHN)(SCH)}], can also be synthesized from the reaction of BH·THF with [PPh{κ-,-(SNCH)}{κ-,,'-BH(SNHC)}Ru], --1c. In stark contrast, when -2b was treated with BHMes (Mes = 2,4,6-trimethyl phenyl) it led to the formation of - and -bis(dihydroborate) complexes [{κ-,,-(NHBMes)Ru(SCH)}], (-4 and -4). Both the complexes have two five-membered [Ru-(H)-B-NCS] ruthenacycles with κ-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.

Citing Articles

Quantifying variation in cooperative B-H bond activations using Os(ii) and Os(iii) κ-,-chelated complexes: same, but different.

Gayen S, Assanar F, Shyamal S, Dorairaj D, Ghosh S Chem Sci. 2024; .

PMID: 39290585 PMC: 11403944. DOI: 10.1039/d4sc05092d.

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