82106-45-4Relevant academic research and scientific papers
A simple and high-yield route to iridium, rhodium, osmium and ruthenium: Nido -6-metalladecaborane compounds
Bould, Jonathan,Clegg, William,Cva?ka, Josef,Londesborough, Michael G. S.,Macías, Ramón,Passarelli, Vincenzo,Waddell, Paul G.
, p. 16751 - 16764 (2021/12/08)
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] (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. This journal is
Ten-vertex Metallaborane Chemistry: Synthesis and Characterization of Some ortho-Cycloboronated nido-5- and -6-Iridadecaboranes; Crystal Structures of and
Bould, Jonathan,Crook, Janet E.,Greenwood, Norman N.,Kennedy, John D.,Thornton-Pett,, Mark.
, p. 1441 - 1450 (2007/10/02)
The arachno-anion - reacts with to give an 80percent yield of the known compound (1), whereas the reaction of nido-- with gives a mixture of products.These have been characterized by a combination of multi-element n.m.r. spectroscopy and single-crystal X-ray diffraction analysis to be (2) (60percent yield), (3) (20percent yield), (4) (0.1-20percent yield) and a = 1254.4(3), b = 1524.6(4), c = 1091.7(2) pm, α = 97.69(2), β = 115.09(2), γ = 88.79(2) deg, and Z = 2.Crystals of the bis(chloroform) solvate of (5) are triclinic, space group P1 with a = 1501.3(3), b = 1571.6(3), and c = 1478.1(3) pm, α = 104.27(2), β = 113.81(2), γ = 97.98(2) deg, and Z = 2.A further compound was isolated and tentatively identified as a phosphine-substituted nido-6-iridadecaborane.A scheme to explain the mixture of products is briefly discussed.
