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Transition‐Metal Complexes Based on the 1,3,5‐Triethynyl Benzene Linking Unit
Author(s) -
Packheiser Rico,
Rüffer Tobias,
Ecorchard Petra,
Lang Heinrich
Publication year - 2010
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201000243
Subject(s) - dehydrohalogenation , transition metal , metal , chemistry , crystallography , stereochemistry , catalysis , organic chemistry
The synthesis of a unique series of heteromultinuclear transition metal compounds is reported. Complexes 1‐I‐3‐Br‐5‐(FcC≡C)‐C 6 H 3 ( 4 ), 1‐Br‐3‐(bpy‐C≡C)‐5‐(FcC≡C)‐C 6 H 3 ( 6 ), 1,3‐(bpy‐C≡C) 2 ‐5‐(FcC≡C)‐C 6 H 3 ( 7 ), 1‐( X C≡C)‐3‐(bpy‐C≡C)‐5‐(FcC≡C)‐C 6 H 3 ( 8 , X = SiMe 3 ; 9 , X = H), 1‐(HC≡C)‐3‐[(CO) 3 ClRe(bpy‐C≡C)]‐5‐(FcC≡C)‐C 6 H 3 ( 11 ), 1‐[(Ph 3 P)AuC≡C]‐3‐[(CO) 3 ClRe(bpy‐C≡C)]‐5‐(FcC≡C)‐C 6 H 3 ( 13 ), 1‐[(Ph 3 P)AuC≡C]‐3‐(bpy‐C≡C)‐5‐(FcC≡C)‐C 6 H 3 ( 14 ), [1‐[(Ph 3 PAuC≡C]‐3‐[{[Ti](C≡CSiMe 3 ) 2 }Cu(bpy‐C≡C)]‐5‐(FcC≡C)‐C 6 H 3 ]PF 6 ( 16 ), and [1,3‐[( t Bu 2 bpy) 2 Ru(bpy‐C≡C)] 2 ‐5‐(FcC≡C)‐C 6 H 3 ](PF 6 ) 4 ( 18 ) (Fc = (η 5 ‐C 5 H 4 )(η 5 ‐C 5 H 5 )Fe, bpy = 2,2′‐bipyridiyl‐5‐yl, [Ti] = (η 5 ‐C 5 H 4 SiMe 3 ) 2 Ti) were prepared by using consecutive synthesis methodologies including metathesis, desilylation, dehydrohalogenation, and carbon–carbon cross‐coupling reactions. In these complexes the corresponding metal atoms are connected by carbon‐rich bridging units comprising 1,3‐diethynyl‐, 1,3,5‐triethynylbenzene and bipyridyl units. They were 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–C C≡C and C≡C bond lengths.