TY - JOUR
T1 - 14 Step-15 electron reversible redox behavior of tetrameric oligomer of oxo-bridged triruthenium cluster
AU - Hamaguchi, Tomohiko
AU - Nagino, Haruko
AU - Hoki, Katsunori
AU - Kido, Hiroaki
AU - Yamaguchi, Tadashi
AU - Breedlove, Brian K.
AU - Ito, Tasuku
PY - 2005/4/15
Y1 - 2005/4/15
N2 - Pyrazine-bridged trimeric and tetrameric oligomers of triruthenium clusters, [{Ru 3O(CH 3CO 2) 6(CO)(Py)}- (μ-pz)-{Ru 3O(CH 3CO 2) 6(CO)}-(μ- pz)-{Ru 3O(CH 3CO 2) 6(py) 2}] + (1), and [{Ru 3O(CH 3CO 2) 6(CO)(py)}-(μ-pz)-{Ru 3O-(CH 3CO 2) 6(CO)}-(μ-pz)-{Ru 3O(CH 3CO 2) 6(py)}-(μ-pz)-{Ru 3O(CH 3CO 2) 6(dmap) 2}] 2+ (2), were prepared (pz = pyrazine, py = pyridine, dmap = 4-dimethylaminopyridine). Trimer 1 and tetramer 2 show closely spaced 11 step-12 electron and 14 step-15 electron reversible redox waves, respectively, in their cyclic voltammograms in CH 3CN. These compounds were designed specifically to incorporate the above-mentioned electrochemical behavior, using the unique redox properties characteristic of triruthenium clusters: (i) each Ru 3 cluster unit generally exhibits four reversible single electron waves from Ru 3 IV,III,III to Ru 3 II,II,II state; (ii) the redox potentials of the cluster units strongly depend on the basicity of the ancillary ligand; (iii) redox potentials of the Ru 3 cluster units vary by 300-500 mV depending on the presence or the absence of a carbonyl ligand on the cluster unit; (iv) in the negative potential region, electronic interaction through the bridging pyrazine between adjacent Ru 3 units containing a carbonyl ligand makes the difference in redox potential of each unit larger. 1 and 2 were synthesized by linking Ru 3 cluster units with the desired ancillary ligand set in the appropriate order.
AB - Pyrazine-bridged trimeric and tetrameric oligomers of triruthenium clusters, [{Ru 3O(CH 3CO 2) 6(CO)(Py)}- (μ-pz)-{Ru 3O(CH 3CO 2) 6(CO)}-(μ- pz)-{Ru 3O(CH 3CO 2) 6(py) 2}] + (1), and [{Ru 3O(CH 3CO 2) 6(CO)(py)}-(μ-pz)-{Ru 3O-(CH 3CO 2) 6(CO)}-(μ-pz)-{Ru 3O(CH 3CO 2) 6(py)}-(μ-pz)-{Ru 3O(CH 3CO 2) 6(dmap) 2}] 2+ (2), were prepared (pz = pyrazine, py = pyridine, dmap = 4-dimethylaminopyridine). Trimer 1 and tetramer 2 show closely spaced 11 step-12 electron and 14 step-15 electron reversible redox waves, respectively, in their cyclic voltammograms in CH 3CN. These compounds were designed specifically to incorporate the above-mentioned electrochemical behavior, using the unique redox properties characteristic of triruthenium clusters: (i) each Ru 3 cluster unit generally exhibits four reversible single electron waves from Ru 3 IV,III,III to Ru 3 II,II,II state; (ii) the redox potentials of the cluster units strongly depend on the basicity of the ancillary ligand; (iii) redox potentials of the Ru 3 cluster units vary by 300-500 mV depending on the presence or the absence of a carbonyl ligand on the cluster unit; (iv) in the negative potential region, electronic interaction through the bridging pyrazine between adjacent Ru 3 units containing a carbonyl ligand makes the difference in redox potential of each unit larger. 1 and 2 were synthesized by linking Ru 3 cluster units with the desired ancillary ligand set in the appropriate order.
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U2 - 10.1246/bcsj.78.591
DO - 10.1246/bcsj.78.591
M3 - Article
AN - SCOPUS:18744404834
SN - 0009-2673
VL - 78
SP - 591
EP - 598
JO - Bulletin of the Chemical Society of Japan
JF - Bulletin of the Chemical Society of Japan
IS - 4
ER -