Transition-Metal Complexes Based on the 1,3,5-Triethynyl Benzene Linking Unit

Heinrich Lang (1)

1 Institut fr Chemie

The synthesis of a unique series of heteromultinuclear transition metal compounds is re-ported. Complexes 1-I-3-Br-5-(FcC≡C)-C6H3 (4), 1-Br-3-(bpy-C≡C)-5-(FcC≡C)-C6H3 (6), 1,3-(bpy-C≡C)2-5-(FcC≡C)-C6H3 (7), 1-(XC≡C)-3-(bpy-C≡C)-5-(FcC≡C)-C6H3 (8, X = SiMe3; 9, X = H), 1-(HC≡C)-3-[(CO)3ClRe(bpy-C≡C)]-5-(FcC≡C)-C6H3 (11), 1-[(Ph3P)Au¬C≡C]-3-[(CO)3ClRe(bpy-C≡C)]-5-(FcC≡C)-C6H3 (13), 1-[(Ph3P)AuC≡C]-3-(bpy-C≡C)-5-(FcC≡C)-C6H3 (14), [1-[(Ph3PAuC≡C]-3-[{[Ti](C≡CSiMe3)2}Cu(bpy-C≡C)]-5-(FcC≡C)-C6H3]PF6 (16), and [1,3-[(t-Bu2bpy)2Ru(bpy-C≡C)]2-5-(FcC≡C)-C6H3](PF6)4 (18) (Fc = (C5H4)(C5H5)Fe, bpy = 2,2'-bipyridiyl-5-yl, [Ti] = (C5H4SiMe3)2Ti) were prepared by using consecutive synthesis methodologies including metathesis, desilylation, dehydrohaloge-nation, and carbon-carbon cross-coupling reactions. In these complexes the corresponding metal atoms are connected via carbon-rich bridging units comprising 1,3-diethynyl-, 1,3,5-triethynylbenzene and bipyridyl units. They have been characterized by elemental analysis, IR and NMR spectroscopy, and partly by ESI-TOF mass spectrometry. The structures of 4 and 11 in the solid state are reported. Both molecules are characterized by the central benzene core bridging the individual transition metal complex fragments. The corresponding acetylide entities are, as typical, found in a linear arrangement with representative M-C, C-CC≡C and C≡C bond distances.

Mots clés: Physical Sciences

Heinrich Lang. Transition-Metal Complexes Based on the 1,3,5-Triethynyl Benzene Linking Unit. Journal of Inorganic and General Chemistry / Zeitschrift für anorganische und allgemeine Chemie, 2010, 636 (15), pp.2607. ⟨10.1002/zaac.201000243⟩. ⟨hal-00574817⟩