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Lookup NU author(s): Professor William Clegg, 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.
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
URL: https://doi.org/10.1039/D1DT02971A
DOI: 10.1039/D1DT02971A
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