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Mixed main group transition metal clusters: Reactions of [Ru 3 (CO) 10 (μ-dppm)] with Ph 3 SnH

Khan, MMM; Ghosh, S; Hogarth, G; Tocher, DA; Richmond, MG; Kabir, SE; Roesky, HW; (2017) Mixed main group transition metal clusters: Reactions of [Ru 3 (CO) 10 (μ-dppm)] with Ph 3 SnH. Journal of Organometallic Chemistry , 840 pp. 47-55. 10.1016/j.jorganchem.2017.03.052. Green open access

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Abstract

Novel dppm-ligated ruthenium-tin clusters have been prepared from the reaction of [Ru3(CO)10(μ-dppm)] with Ph3SnH. At room temperature and in the presence of Me3NO, [Ru3(CO)9(SnPh3) (μ-dppm) (μ-H)] (1) is produced from the formal loss of CO and Sn-H bond oxidative-addition. Treatment of 1 with a further two equivalents of Ph3SnH (in the presence of Me3NO) gave [Ru3(CO)7(SnPh3)2(μ-SnPh2)(μ-dppm)(μ-H)(μ3-H)] (2) which results from both Sn–H and Sn–C bond scission and contains two different hydride environments (μ and μ3) and a μ-SnPh2 moiety. Cluster 2 has 48 CVE (cluster valence electron) with three formal ruthenium-ruthenium bonds; two of those are very long and fall at the extreme end of distances attributed to ruthenium-ruthenium bonds. Thermolysis of 2 at 66 °C liberates benzene to give [Ru3(CO)8(SnPh3)(μ-SnPh2)(μ3-SnPh2)(μ-dppm)(μ-H)] (3). DFT calculations confirm that the hydride bridges one of the Ru-μ-SnPh2 bonds in 3. The solid-state structures of 2 and 3 have been determined by X-ray crystallography, and the bonding and ligand distribution have been investigated by DFT studies. The geometry-optimized structures are consistent with the solid-state structures.

Type: Article
Title: Mixed main group transition metal clusters: Reactions of [Ru 3 (CO) 10 (μ-dppm)] with Ph 3 SnH
Open access status: An open access version is available from UCL Discovery
DOI: 10.1016/j.jorganchem.2017.03.052
Publisher version: https://doi.org/10.1016/j.jorganchem.2017.03.052
Language: English
Additional information: This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions.
Keywords: Triruthenium clusters; Triphenyltin activation; Diphosphine ligand; DFT
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: https://discovery.ucl.ac.uk/id/eprint/1554650
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