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標題: Nucleophilic substitution reactions of acetylides on substituted tricarbonyl(eta(6)-fluoroarene)chromium and reactions of tricarbonyl eta(6)-(2-trimethylsilylethynyl) toluene chromium and tricarbonyl eta(6)-(p-ethynylphenylethynyl)benzene chromium with di
作者: Hong, F.E.
Liaw, J.W.
Chien, B.J.
Chang, Y.C.
Lin, C.C.
Wang, S.L.
Liao, F.L.
關鍵字: nucleophilic substitution;mu-alkyne bridged bimetallic compounds;chromium;cobalt;tele-substitution;arenetricarbonylchromium complexes;aromatic-substitution;conducting polymers;hydrogen migration;tricarbonyl;commerce;cine
Project: Polyhedron
期刊/報告no:: Polyhedron, Volume 18, Issue 21, Page(s) 2737-2747.
Nucleophilic substitution reactions of various acetylides on substituted tricarbonyl(eta(6)-fluoroarene)chromiums were pursued. The reaction presumably underwent a more complicated mechanism rather than the direct substitution on the fluorine-bearing carbon. The organometallic compounds (eta(6)-(C6H3RRR3)-R-1-R-2)Cr(CO)(3) (R-1: C=C-C6H4CH3, R-2: o-Me, R-3: H (5a), R-1: C=C-C6H4CH3, R-2: o-OMe, R-3: H (6a), R-1: C=C-C6H4CH3, R-2: m-OMe, R-3: H (6b), R-1: C=CPh, R-2: o-Me, R-3: o-OMe (8b), R-1: C=CPh, R-2: m-Me, R-3: m-OMe (8c), R-1: C=CSiMe3, R-2: o-Me, R-3: H (9a), R-1: C=C-C6H4C=CH, R-2: H, R-3: H (12), R-1: C=C-C6H4C=CH, R-2: o-Me, R-3: H (13)) as well as the organometallic dimmer [{(eta(6)-o-Me-C6H4)Cr(CO)(3)(di-ethynyl)] (di-ethynyl: C=C-C6H4C=C (14)) have been synthesized from nucleophilic substitution reactions of tricarbonyl(eta(6)-fluoroarene)(chromium) compounds with suitable acetylides. The products have been characterized by spectroscopic means. In addition, (8b) and (8c) were characterized by X-ray diffraction studies. Further reactions of (9a) and (12) with appropriate amount of Co-2(CO)(8) yielded mu-alkyne bridged bimetallic complexes, Co-2(CO)(6){mu-Me3SiC=C-(o-tolueneCr(CO)(3)} (10) and (Co-2(CO)(6))(2){mu-HC=C-C6H4-C=C-(benzene)Cr(CO)(3))}(15), respectively. Both (10) and (15) were characterized by spectroscopic means as well as single crystal X-ray crystallography. The core of these molecules is quasi-tetrahedron containing a Co2C2 unit. A two-dicobalt-fragments coordinated di-enyls complex, (Co-2(CO)(6))(2){mu-HC=C-C6H4-C=C-H} (17), was synthesized from the reaction of 1,3-diethynylbenzene with Co-2(CO)(8). Crystallographic studies of (17) show that it exhibits a distorted Co2C2 quasi-tetrahedral geometry. (C) 1999 Elsevier Science Ltd. All rights reserved.
ISSN: 0277-5387
DOI: 10.1016/s0277-5387(99)00186-2
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