TY - JOUR
T1 - Bis(η6-hexamethylbenzene)(η6,η6-[2n]cyclophane)diruthenium-(11,11) Complexes and Their Two-Electron Reduction to [2n]Cyclophane Derivatives Having Two Cyclohexadienyl Anion Decks Joined by an Extremely Long Carbon-Carbon Bond
AU - Plitzko, Klaus Dieter
AU - Rapko, Brian
AU - Collas, Bernhard
AU - Wehrle, Gabriele
AU - Weakley, Timothy
AU - Pierce, David T.
AU - Geiger, William E.
AU - Haddon, Robert C.
AU - Boekelheide, Virgil
PY - 1990/1
Y1 - 1990/1
N2 - series of bis(i;6-hexamethylbenzene)(η6,η6-[2,l]cyclophane)diruthenium(II, II) tetrakis(tetrafluoroborate) complexes, 4, 5, 9, 10, and 11, has been prepared, where the [2n] cyclophanes are [22](l,4)cyclophane, [22](l,3)cyclophane, 4,7,13,16-tetramethyl-[22](1,4)cyclophane, 4,5,7,8-tetramethyl-[22](l,4)cyclophane, and [23](l,3,5)cyclophane, respectively. These 4+ diruthenium complexes undergo two-electron reduction to give 7, 8,12,13, and 14, respectively, in which each of the cyclophane ligands now has two cyclohexadienyl anion decks connected by a new carbon-carbon bond. The assignment of structures to these two-electron reduction products is based on 1H and 13C NMR spectralanalyses, electrochemical studies, and X-rayphotoelectron data. A single-crystal X-ray analysis confirmed the structure assigned to the [22](l,4)cyclophane derivative 7 and showed that the carbon-carbon bond connecting the two cyclohexadienyl anion decks in 7 is 1.96 (3) Å in length, an extremely long carbon-carbon bond. A theoretical analysis of these 2+ diruthenium complexes and their formation is presented.
AB - series of bis(i;6-hexamethylbenzene)(η6,η6-[2,l]cyclophane)diruthenium(II, II) tetrakis(tetrafluoroborate) complexes, 4, 5, 9, 10, and 11, has been prepared, where the [2n] cyclophanes are [22](l,4)cyclophane, [22](l,3)cyclophane, 4,7,13,16-tetramethyl-[22](1,4)cyclophane, 4,5,7,8-tetramethyl-[22](l,4)cyclophane, and [23](l,3,5)cyclophane, respectively. These 4+ diruthenium complexes undergo two-electron reduction to give 7, 8,12,13, and 14, respectively, in which each of the cyclophane ligands now has two cyclohexadienyl anion decks connected by a new carbon-carbon bond. The assignment of structures to these two-electron reduction products is based on 1H and 13C NMR spectralanalyses, electrochemical studies, and X-rayphotoelectron data. A single-crystal X-ray analysis confirmed the structure assigned to the [22](l,4)cyclophane derivative 7 and showed that the carbon-carbon bond connecting the two cyclohexadienyl anion decks in 7 is 1.96 (3) Å in length, an extremely long carbon-carbon bond. A theoretical analysis of these 2+ diruthenium complexes and their formation is presented.
UR - http://www.scopus.com/inward/record.url?scp=2542483938&partnerID=8YFLogxK
U2 - 10.1021/ja00174a015
DO - 10.1021/ja00174a015
M3 - Article
AN - SCOPUS:2542483938
SN - 0002-7863
VL - 112
SP - 6545
EP - 6556
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 18
ER -