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A Reversible NO-Triggered Multiple Metallaborane Cluster Fusion by Ligand Expulsion/Addition from (PMe2Ph)4Pt2B10H10 to Afford (PMe2Ph)8Pt8B40H40 and (PMe2Ph)5Pt4B20H20

Lookup NU author(s): Emeritus Professor Bill CleggORCiD, Dr Paul Waddell



This is the authors' accepted manuscript of an article that has been published in its final definitive form by American Chemical Society, 2020.

For re-use rights please refer to the publisher's terms and conditions.


© 2020 American Chemical Society. The dimetallic boron hydride cluster, (PMe2Ph)4Pt2B10H10 (1-Pt2), is known to reversibly sequester small molecules (e.g., O2, CO, and SO2) across its Pt-Pt cluster vector. Here, we report the very different effect of the addition of nitric oxide (NO) to solutions of (1-Pt2) that prompts the elimination of some of its phosphine ligands and the autofusion of the resultant {(PMe2Ph)xPt2B10H10} units to afford the metallaborane conglomerates (PMe2Ph)8Pt8B40H40 (2-Pt8, 38%) and (PMe2Ph)5Pt4B20H20 (3-Pt4, 34%). Single-crystal X-ray studies of these multicluster assemblies reveal the links between the clusters to be a combination of both Pt-Pt bonds and Pt-μH-B 2-electron, 3-center bonds in (2-Pt8) and Pt-μH-B 2-electron, 3-center bonds in (3-Pt4). For compound (2-Pt8), the cluster assemblage can be effectively reversed by the addition of ethyl isonitrile (EtNC) to afford (EtNC)3(PMe2Ph)2Pt2B10H10 4 in quantitative yield. The compounds were characterized by mass spectrometry, multielement NMR spectroscopy, and single-crystal X-ray diffraction studies.

Publication metadata

Author(s): Bould J, Clegg W, Waddell PG, Cvacka J, Dusek M, Londesborough MGS

Publication type: Article

Publication status: Published

Journal: Inorganic Chemistry

Year: 2020

Volume: 59

Issue: 7

Pages: 5030-5040

Print publication date: 06/04/2020

Online publication date: 24/03/2020

Acceptance date: 23/01/2020

Date deposited: 12/03/2020

ISSN (print): 0020-1669

ISSN (electronic): 1520-510X

Publisher: American Chemical Society


DOI: 10.1021/acs.inorgchem.0c00247


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