Preparation of closo-10-vertex transition metal carbaboranes

Sˇtibr, Bohumil; Janousˇek, Zbyneˇk; Basˇe, Karel; Dolanský, J.; Herˇmánek, Stanislav; Солнцев, К. А.; Butman, L. A.; Kiznetsov, Igor I.; Кузнецов, Н. Т.

doi:10.1016/0277-5387(82)80016-8

Cited by 19 publications

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“…Although metallacarboranes with a { closo -MCB 8 } architecture are known, 10b, they are relatively rare. These are limited primarily to clusters with 2,1- and 6,1-MCB 8 atom arrangements; we are aware of only one example 18a,b,f with a {10,1-MCB 8 } architecture.…”

Section: Resultsmentioning

confidence: 99%

Ten-Vertex Iron−Monocarbollide Complexes: Synthesis and Reactivity of the Anion [4,9-{Fe(CO)₄}-9,9,9-(CO)₃-arachno-9,6-FeCB₈H₁₁]^-

2006

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The reagent [arachno-4-CB8H14] reacts with [Fe3(CO)12] in tetrahydrofuran (THF) at reflux temperatures, followed by addition of [N(PPh3)2]Cl, to afford [N(PPh3)2][4,9-{Fe(CO)4}-9,9,9-(CO)3-arachno-9,6-FeCB8H11] (3). In the anion of 3, one iron atom is part of the open CBBFeBB face of a 10-vertex {arachno-9,6-FeCB8} cage, to which the second iron atom is attached via an Fe-Fe bond and an additional exo-polyhedral Fe-B sigma bond. Upon heating 3 in refluxing toluene, the closed 10-vertex species [N(PPh3)2][2,2,2-(CO)3-closo-2,1-FeCB8H9] (4) is obtained, whereas the isomeric compound [N(PPh3)2][6,6,6-(CO)3-closo-6,1-FeCB8H9] (5) is isolated upon heating [closo-4-CB8H9]- and [Fe3(CO)12] in refluxing THF with subsequent addition of [N(PPh3)2]Cl. Protonation of 3 using CF3SO3H in CH2Cl2 gives the charge-compensated compound [4,9-{Fe(CO)4}-4-(mu-H)-9,9,9-(CO)3-arachno-9,6-FeCB8H11] (6), in which the B-Fe sigma bond of the precursor has been converted to a B-H right harpoon-up Fe linkage. In contrast, 3 with {M(PPh3)}+ gives the trimetallic species [1,3,4,9-{MFe(CO)4(PPh3)}-1,3-(mu-H)2-9,9,9-(CO)3-arachno-9,6-FeCB8H9] (M = Cu (7), Ag 8) in which the three metal centers form a V-shaped M-Fe-Fe unit. Compound 6 reacts with PEt3 in the presence of Me(3)NO to yield [4,9-(PEt3)2-9,9-(CO)2-nido-9,6-FeCB8H10] (9). In the latter, the formerly exo-polyhedral {Fe(CO)4} fragment has been replaced by a PEt3 ligand, with a second PEt3 substituting one CO group at the remaining cluster iron vertex. The novel structural features of compounds 3-9 have been confirmed by single-crystal X-ray diffraction studies.

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Section: Resultsmentioning

confidence: 99%