Carbonyl–metal fragment insertion into eight-vertex [closo-1-CB₇H₈]⁻. Facile synthesis of ten-vertex metalladicarbollide complexes [2,2,2-(CO)₃-1-OH-closo-2,1,10-MC₂B₇H₈]n⁻{M = Fe, Ru (n = 0), Mn, Re (n = 1)}

Abstract

Insertion of {M(CO)4} fragments (M = Fe, Ru, Mn, Re) into the eight-vertex monocarborane anion [closo-1-CB7H8]- affords ten-vertex metal-dicarbollide complexes.

Incremental iodination of the eight-vertex closo monocarborane anion [closo-1-CB7H8]–: Preparation and characterization of [closo-1-CB7H5-6,7,8-I3]– and [closo-1-CB7H2-2,3,4,6,7,8-I6]–, and the synthesis of the first eight-vertex C-methylated carborane anion [1-CH3-closo-1-CB7H4-6,7,8-I3]–

“…This study documented the insertion of metal fragments into the {CB 7 } structure of 1 and, indeed, the incorporation of a carbon atom from the carbonylmetal ligand to give a unique {nido-1,9-C 2 B 7 } moiety 15 . These new metallacarboranes were structurally characterized by single-crystal X-ray diffraction [15][16][17] , but the precise structure of anion 1 itself is still not clear. As yet, no single-crystal X-ray structure of the parent anion exists, but its static solid-state cluster structure is presumed to be as I shown in Scheme 1.…”

“…[closo-1-CB 7 H 8 ] -has recently been shown to be a versatile reagent in the formation of carborane-transitional metal complexes on reaction with a series of metal carbonyls ({M(CO) 4 } where M = Fe, Ru, Mn, Re) [15][16][17] . This study documented the insertion of metal fragments into the {CB 7 } structure of 1 and, indeed, the incorporation of a carbon atom from the carbonylmetal ligand to give a unique {nido-1,9-C 2 B 7 } moiety 15 .…”

Boron, aluminium, gallium, indium and thallium

“…30 Reaction of the closo-carborane anion [CB 7 H 8 ] À with metal carbonyl sources (i.e., Fe 2 (CO) 9 , Ru 3 (CO) 12 , Mn 2 (CO) 10 and Re 2 (CO) 10 ) results in the novel insertion of CO into the cluster framework and formation of a series of {C-OH} substituted (8), or PEt 3 , n = 0; M = Ru or Re L = CO, n = 0; M = Mn, L = CO, n = 1). 31 The arachno-metallacarborane system [4,9-{Fe(CO) 4 }-9,9,9-(CO) 3 -arachno-9,6-FeCB 8 H 11 ][N(PPh 3 ) 2 ](9) has been synthesised from the reaction of [arachno-CB 8 H 14 ] with Fe 3 (CO) 12 . Subsequent reactions of the bimetallic complex; thermolysis, protonation substitution reactions and metallation with {CuPPh 3 } or {AgPPh 3 } have been described.…”

Manganese, technetium and rhenium

“…Ten-vertex metal-dicarbollide complexes of the form [2,2,2-(CO) 3 -1-OH-closo-2,1,10-MnC 2 B 7 H 8 ] À have been easily prepared by insertion of {Mn(CO) 4 } fragments into the eight-vertex monocarborane anion [closo-1-CB 7 H 8 ] À . 1 Two new, m 2 -dicarboxylato-bridged manganese Schiff base complexes, [Mn 2 (C 13 H 9 N 2 O 2 ) 2 (NCS) 2 ] 2À and [Mn(C 19 H 20 N 2 O 4 )(N 3 )(H 2 O)] 2À have been prepared and structures of both complexes characterised by single-crystal X-ray analysis. 2 Single-crystalline Mn 2 SnO 4 nanowires have been synthesised by chemical vapour deposition and found to have a ferromagnetic phase below 46 K, probably due to the presence of Mn 3+ ions at octahedral sites.…”