TY - JOUR
T1 - Dinuclear Cu(I) complexes of 1,2,4,5-tetra(7-azaindolyl)benzene
T2 - Persistent 3-coordinate geometry, luminescence, and reactivity
AU - Zhao, Shu Bin
AU - Wang, Rui Yao
AU - Wang, Suning
PY - 2006/7/24
Y1 - 2006/7/24
N2 - Five Cu(I) complexes [Cu2(ttab)(CH3CN) 2][BF4]2 (1), [Cu2(ttab)(PPh 3)2][BF4]2 (2), [Cu 2(ttab)I2] (3), [Cu2(ttab)(I3) 2] (4), and [Cu2(ttab)(I)BF4]n (5) with 1,2,4,5-tetra(7-azaindolyl)benzene (ttab) have been synthesized and characterized. The structures of compound 1, 2, 4, and 5 have been determined by single-crystal X-ray diffraction analyses, which established that 1, 2, and 4 are discrete dinuclear Cu2 compounds while compound 5 is a 1D coordination polymer with the I- ligand bridging two dinuclear Cu2 units. The ttab ligand in all four complexes adopts a 1,3-chelation mode. The Cu(I) center in all complexes is three-coordinate. Close contact between the Cu(I) center and the benzene ring in the ttab ligand was observed in all four structures, which is believed to play a role in stabilizing the three-coordinate geometry of the Cu(I) center. The crystals of 1, 2, and 5 contain channels in the lattice that host solvent molecules such as CH 2Cl2 and toluene. Fluorescent measurements established that, in solution, compounds 1-3 display weak blue luminescence which originates from the ttab but is significantly red-shifted and has a much lower emission intensity, compared to the free ttab ligand. The application of compound 1 in C-N cross-coupling reactions was examined by using the reaction of phenyl halides with imidazole as a model system. For the reaction with phenyl iodide, 1 was found to be as effective a catalyst as the CuI/1,10-phenanthroline system. For the reaction with phenyl bromide, 1 is less effective than the CuI/1,10-phenanthroline system. Compound 1 reacts with O2 gas, as established by UV-vis spectra, but the oxidized products have not been characterized.
AB - Five Cu(I) complexes [Cu2(ttab)(CH3CN) 2][BF4]2 (1), [Cu2(ttab)(PPh 3)2][BF4]2 (2), [Cu 2(ttab)I2] (3), [Cu2(ttab)(I3) 2] (4), and [Cu2(ttab)(I)BF4]n (5) with 1,2,4,5-tetra(7-azaindolyl)benzene (ttab) have been synthesized and characterized. The structures of compound 1, 2, 4, and 5 have been determined by single-crystal X-ray diffraction analyses, which established that 1, 2, and 4 are discrete dinuclear Cu2 compounds while compound 5 is a 1D coordination polymer with the I- ligand bridging two dinuclear Cu2 units. The ttab ligand in all four complexes adopts a 1,3-chelation mode. The Cu(I) center in all complexes is three-coordinate. Close contact between the Cu(I) center and the benzene ring in the ttab ligand was observed in all four structures, which is believed to play a role in stabilizing the three-coordinate geometry of the Cu(I) center. The crystals of 1, 2, and 5 contain channels in the lattice that host solvent molecules such as CH 2Cl2 and toluene. Fluorescent measurements established that, in solution, compounds 1-3 display weak blue luminescence which originates from the ttab but is significantly red-shifted and has a much lower emission intensity, compared to the free ttab ligand. The application of compound 1 in C-N cross-coupling reactions was examined by using the reaction of phenyl halides with imidazole as a model system. For the reaction with phenyl iodide, 1 was found to be as effective a catalyst as the CuI/1,10-phenanthroline system. For the reaction with phenyl bromide, 1 is less effective than the CuI/1,10-phenanthroline system. Compound 1 reacts with O2 gas, as established by UV-vis spectra, but the oxidized products have not been characterized.
UR - http://www.scopus.com/inward/record.url?scp=33746932854&partnerID=8YFLogxK
U2 - 10.1021/ic060237h
DO - 10.1021/ic060237h
M3 - Article
C2 - 16841988
AN - SCOPUS:33746932854
SN - 0020-1669
VL - 45
SP - 5830
EP - 5840
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 15
ER -