| Title
| - Synthesis of 16-Electron (η3-Cyclooctenyl)metallacarboranes ofRhodium(III) and Iridium(III) with the New Sterically Demanding[(4‘-MeC6H4)2C2B9H9]2- Carborane Ligand. Molecular Structures of[3-{(1−3-η3)-C8H13}-1,2-(4‘-MeC6H4)2-3,1,2-pseudocloso-MC2B9H9](M = Rh, Ir) and [(η6-MeC6H4)Rh(C2B9H9C6H4Me)Rh(η4-C8H12)]2, aDimeric Byproduct Containing Distorted 13-Vertex{4,9,1,10-Rh2C2B9} Cluster Units
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| Abstract
| - Reactions of the [K]+ salt of the [7,8-(4‘-MeC6H4)2-7,8-nido-C2B9H10]- monoanion with the COD−rhodium and COD−iridium μ-chloride complexes [(η4-COD)2M2(μ-Cl)2] proceed in benzene at ambienttemperature with the formation of the 16-electron complexes [3-{(1−3-η3)-C8H13}-1,2-(4‘-MeC6H4)2-3,1,2-pseudocloso-MC2B9H9] (5, M = Rh(III); 6, M = Ir(III)), respectively, whose pseudocloso strucrurehas been confirmed by single-crystal X-ray diffraction studies. The major species 5 is formed along witha small amount of the dimeric rhodacarborane [(η6-MeC6H4)Rh(C2B9H9C6H4Me)Rh(η4-C8H12)]2 (7), which, asfound from X-ray structure determinations, is composed of two distorted {4,9,1,10-Rh2C2B9} clusterunits joined together through η6 coordination of the 4-tolyl cage substituent of one unit to one of therhodium atoms of the second unit and vice versa.
- Reaction between [K][7,8-(4‘-MeC6H4)2-7,8-nido-C2B9H10] and [(η4-COD)2M2(μ-Cl)2] (M = Rh, Ir) in benzene affords the two new formally 16-electron pseudocloso-metallacarboranes [3-(η3-C8H13)-1,2-(4‘-MeC6H4)2-3,1,2-pseudocloso-MC2B9H9] (M = Rh(III), Ir(III)), respectively, along with the dimeric 13-vertex rhodacarborane [(η6-MeC6H4)Rh(C2B9H9C6H4Me)Rh(η4-C8H12)]2 (7) as a byproduct. The new complexes 5−7 were all characterized by NMR spectroscopy as well as by single-crystal X-ray diffraction studies.
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