Synthesis,structures, photophysical properties,and catalytic characteristics of 2,9-dimesityl-1,10-phenanthroline (dmesp) transition metal complexes |
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| Authors: | M. Mustafa Cetin Sara Shafiei-Haghighi Jiazhen Chen Sheng Zhang Amanda C. Miller Daniel K. Unruh Dominick J. Casadonte Jr Tracy L. Lohr Tobin J. Marks Michael F. Mayer J. Fraser Stoddart Michael Findlater |
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| Affiliation: | 1. Department of Chemistry, Northwestern University, Evanston, Illinois;2. Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas;3. Department of Chemistry, Northwestern University, Evanston, Illinois Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois |
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| Abstract: | The syntheses of the 2,9-dimesityl-1,10-phenanthroline ( dmesp ) metal complexes, [Cu(dmesp)(MeCN)]PF6 ( 1 ), [Cu(dmesp)2]PF6 ( 2 ), Fe(dmesp)Cl2 ( 3 ), Co(dmesp)Cl2 ( 4 ), Ni(dmesp)Cl2 ( 5 ), Zn(dmesp)Cl2 ( 6 ), Pd(dmesp)MeCl ( 7 ), Cu(dmesp)Cl ( 8 ), and Pd(dmesp)2Cl2 ( 9 ), in good to high yields are described. These complexes were characterized by 1H and 13C NMR spectroscopy, HR–MS (ESI and/or APPI), and elemental analysis (CHN). The solid-state structures of complexes 1 – 8 were determined by single-crystal X-ray analysis and their photophysical properties were also characterized. To demonstrate the versatility of this new platform, complexes 3 – 5 , 8 , and 9 were employed in the catalytic oligomerization of ethylene using modified methyl aluminoxane (MMAO) as the cocatalyst, where Co(II) and Ni(II) complexes ( 4 and 5 , respectively) were found to exhibit moderate selectivity for catalytic dimerization of ethylene to butenes over tri- or tetramerization. Complex 8 is an effective catalyst of both the commonly encountered “click” reaction and amine arylation chemistries. Complexes 6 and 9 were found to be excellent catalysts for Friedel-Crafts alkylation and Suzuki-Miyaura coupling, respectively. |
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| Keywords: | catalysis oligomerization phenanthroline transition metals |
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