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A simple and high-yield route to iridium, rhodium, osmium and ruthenium nido-6-metalladecaborane compounds

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 Royal Society of Chemistry, 2021.

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We report a high-yield heterogeneous solid/liquid phase synthetic method to a series of nido-6-metalladecaboranes. The hydridoirida– and hydridorhoda–decaboranes, [6,6,6-H(PPh3)2-nido-6-MB9H13] [M = Ir (1), Rh (2)] are isolatable in 98 % yields from the reaction of the square-planar M(I) complexes, [MCl(PPh3)3] (M = Rh, Ir), with K[B9H14]. The same synthetic procedure but using [MCl(CO)H(PPh3)3] (M = Ru, Os) as metal starting reagents produces the CO-ligated clusters, [6,6,6- (CO)(PPh3)2-nido-6-MB9H13] [M = Ru (3), Os (4)], in yields of 83% and 95%, respectively. These highly convenient syntheses permit the investigation of the reaction chemistry of the new nido-6-metalladecaboranes. Thus, the CO-ligated compounds, 3 and 4, react with the square-planar platinum(II) complex, [PtCl2(PMe2Ph)2], in the presence of potassium triethylborohydride, to give the bimetallic clusters, [1,1,1-(CO)H(PPh3)-isocloso-1-RuB9H8-µ-(1,2)-{Pt(PMe2Ph)2}] (5) and [7,7- (PMe2Ph)2-9,9,9-(CO)(PPh3)2-nido-7,9-PtOsB9H11].CH2Cl2 (6), and the monometallic nido-5-osamadecaborane, [5,5,5-(PPh3)2(CO)-nido-5-OsB9H13] (7). This reactivity illustrates the potential of polyhedral boron-based clusters as molecular scaffolds (“B-frames”) for the construction of multimetallic species. Single-crystal X-ray diffraction analyses have revealed the molecular structures of 3, 5, 6 and 7; the compounds are also studied by multielement NMR spectroscopy, mass spectrometry, IR spectroscopy, and in some cases computationally. Futhermore, the rotation of the {M(X)(PR3)2} moiety (X = H, CO), as PH3-ligated models, is studied by means of DFT-calculated relaxed potential energy surface scans, giving some insight into the lability of the metal-to-borane fragment interaction and of the exo-polyhedral ligands.

Publication metadata

Author(s): Bould J, Londesborough MGS, Passarelli V, Clegg W, Waddell PG, Cvacka J, Macias R

Publication type: Article

Publication status: Published

Journal: Dalton Transactions

Year: 2021

Volume: 50

Issue: 45

Pages: 16751-16764

Online publication date: 03/11/2021

Acceptance date: 01/11/2021

Date deposited: 02/11/2021

ISSN (print): 1477-9226

ISSN (electronic): 1477-9234

Publisher: Royal Society of Chemistry


DOI: 10.1039/D1DT02971A


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