TY - JOUR
T1 - Topological transformation of a trefoil knot into a [2]catenane
AU - Prakasam, Thirumurugan
AU - Bilbeisi, Rana A.
AU - El-Khoury, Roberto
AU - Charbonnière, Loïc J.
AU - Elhabiri, Mourad
AU - Esposito, Gennaro
AU - Olsen, John Carl
AU - Trabolsi, Ali
N1 - Publisher Copyright:
© 2017 The Royal Society of Chemistry.
PY - 2017
Y1 - 2017
N2 - Topological transformation of a zinc-templated trefoil knot, Zn-TK, into a zinc-templated [2]catenane, Zn-[2]C, was studied. The net reaction 2 Zn-TK → 3 Zn-[2]C was accomplished in 89% yield by heating a solution of Zn-TK in D2O. Kinetic investigation by 1H NMR spectroscopy and high resolution mass spectrometry revealed that the mechanism is complex, involving a large pool of intermediates that form after imine bond cleavage. Bromide ions, which can occupy the central cavity of Zn-TK, inhibited the reaction. Two similar transformations were also studied, one of a cadmium-containing trefoil knot, Cd-TK, into a cadmium-containing catenane, Cd-[2]C, and the other of Cd-TK into Zn-[2]C. The latter transformation could be achieved in one step at high temperature or in two steps via transmetallation to form Zn-TK at room temperature followed by topological conversion of Zn-TK to Zn-[2]C at high temperature.
AB - Topological transformation of a zinc-templated trefoil knot, Zn-TK, into a zinc-templated [2]catenane, Zn-[2]C, was studied. The net reaction 2 Zn-TK → 3 Zn-[2]C was accomplished in 89% yield by heating a solution of Zn-TK in D2O. Kinetic investigation by 1H NMR spectroscopy and high resolution mass spectrometry revealed that the mechanism is complex, involving a large pool of intermediates that form after imine bond cleavage. Bromide ions, which can occupy the central cavity of Zn-TK, inhibited the reaction. Two similar transformations were also studied, one of a cadmium-containing trefoil knot, Cd-TK, into a cadmium-containing catenane, Cd-[2]C, and the other of Cd-TK into Zn-[2]C. The latter transformation could be achieved in one step at high temperature or in two steps via transmetallation to form Zn-TK at room temperature followed by topological conversion of Zn-TK to Zn-[2]C at high temperature.
UR - http://www.scopus.com/inward/record.url?scp=85037646156&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85037646156&partnerID=8YFLogxK
U2 - 10.1039/c7dt03582a
DO - 10.1039/c7dt03582a
M3 - Article
C2 - 29147692
AN - SCOPUS:85037646156
SN - 1477-9226
VL - 46
SP - 16474
EP - 16479
JO - Dalton Transactions
JF - Dalton Transactions
IS - 47
ER -