Abstract
Abstract Irradiation of tricarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)manganese (1) in tetrahydrofuran (THF) at 208 K affords the carmine solvent complex dicarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)(THF)manganese (2). Complex 2 thermally reacts with acetylene (3) to give tricarbonyl(η3:2-1,3-dimethyl-bicyclo[3.3.1]-3,6-nonadien-2-yl)manganese (4) and dicarbonyl(5-7,10-13-η-6,8-dimethyl-1,3,5,8,10,12-tridecahexaen-5-yl)manganese (5). The crystal structure of complex 4 was determined at room temperature [triclinic space group P 1 ¯ , $P\bar 1,$ a =7.6891(9), b =8.3860(8), c =10.5252(13) Å, α =93.000(9)°, β =93.390(10)°, γ = 108.032(8)°, V =642.43(13) Å3]. The manganese atom is trigonal-bipyramidally coordinated by three carbonyl ligands, one ethenylic and one allylic fragment. Consequently, the bicyclic olefin ligand 1,3-dimethyl-bicyclo[3.3.1]-3,6-nonadiene coordinates the manganese atom in a η3:2 mode. The constitution of complex 5 was deduced from IR data, elemental analysis, and 1H NMR spectra. For the formation of complexes 4 and 5, a reaction mechanism is proposed.
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