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

0548676 - ÚACH 2022 RIV GB eng J - Journal Article
Bould, Jonathan - Londesborough, Michael Geoffrey Stephen - Passarelli, V. - Clegg, W. - Waddell, P. G. - Cvačka, Josef - Macias, R.
A simple and high-yield route to iridium, rhodium, osmium and ruthenium nido-6-metalladecaborane compounds.
Dalton Transactions. Roč. 50, č. 45 (2021), s. 16751-16764. ISSN 1477-9226. E-ISSN 1477-9234
R&D Projects: GA ČR(CZ) GA18-20286S
Institutional support: RVO:61388980 ; RVO:61388963
Keywords : 10-vertex metallaborane chemistry * nuclear-magnetic-resonance * polyhedral ruthenaborane chemistry * containing cluster chemistry
OECD category: Inorganic and nuclear chemistry; Analytical chemistry (UOCHB-X)
Impact factor: 4.569, year: 2021
Method of publishing: Limited access
https://doi.org/10.1039/D1DT02971A

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-mu-(1,2)-{Pt(PMe2Ph)(2)}] (5) and [7,7-(PMe2Ph)(2)-9,9,9-(CO)(PPh3)(2)-nido-7,9-PtOsB9H11] (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.
Permanent Link: http://hdl.handle.net/11104/0324731


Research data: RSC Publishing, CCDC