Matches in SemOpenAlex for { <https://semopenalex.org/work/W2334607237> ?p ?o ?g. }
- W2334607237 endingPage "9225" @default.
- W2334607237 startingPage "9214" @default.
- W2334607237 abstract "Oxygen activation by copper(I) complexes with tetra- or pentadentate mono- or dinucleating bispidine ligands is known to lead to unusually stable end-on-[{(bispidine)Cu}2(O2)]2+ complexes (bispidines are methyl-2,4-bis(2-pyridin-yl)-3,7-diazabicyclo-[3.3.1]-nonane-9-diol-1,5-dicarboxylates); catecholase activity of these dinuclear CuII/I systems has been demonstrated experimentally, and the mechanism has been thoroughly analyzed. The present density functional theory (DFT) based study provides an analysis of the electronic structure and catalytic activity of [{(bispidine)Cu}2(O2)]2+. As a result of the unique square pyramidal coordination geometry, the dx2–y2 ground state leads to an unusual σ/π bonding pattern, responsible for the stability of the peroxo complex and the observed catecholase activity with a unique mechanistic pathway. The oxidation of catechol to ortho-quinone (one molecule per catalytic cycle and concomitant formation of one equivalent of H2O2) is shown to occur via an associative, stepwise pathway. The unusual stability of the end-on-peroxo-dicopper(II) complex and isomerization to copper(II) complexes with chelating catecholate ligands, which inhibit the catalytic cycle, are shown to be responsible for an only moderate catalytic activity." @default.
- W2334607237 created "2016-06-24" @default.
- W2334607237 creator A5011497765 @default.
- W2334607237 creator A5018905339 @default.
- W2334607237 creator A5021616039 @default.
- W2334607237 creator A5053969983 @default.
- W2334607237 date "2012-08-21" @default.
- W2334607237 modified "2023-09-27" @default.
- W2334607237 title "Structure, Bonding, and Catecholase Mechanism of Copper Bispidine Complexes" @default.
- W2334607237 cites W1524179749 @default.
- W2334607237 cites W1535193939 @default.
- W2334607237 cites W1540454192 @default.
- W2334607237 cites W1963484597 @default.
- W2334607237 cites W1964801890 @default.
- W2334607237 cites W1965249399 @default.
- W2334607237 cites W1966502704 @default.
- W2334607237 cites W1968415097 @default.
- W2334607237 cites W1970549136 @default.
- W2334607237 cites W1972591842 @default.
- W2334607237 cites W1977925490 @default.
- W2334607237 cites W1978412128 @default.
- W2334607237 cites W1978531155 @default.
- W2334607237 cites W1981373094 @default.
- W2334607237 cites W1984184890 @default.
- W2334607237 cites W1984455831 @default.
- W2334607237 cites W1988306316 @default.
- W2334607237 cites W1994533504 @default.
- W2334607237 cites W1995241084 @default.
- W2334607237 cites W1996983535 @default.
- W2334607237 cites W1997785740 @default.
- W2334607237 cites W1998018235 @default.
- W2334607237 cites W1999418142 @default.
- W2334607237 cites W2003004890 @default.
- W2334607237 cites W2005234903 @default.
- W2334607237 cites W2008584788 @default.
- W2334607237 cites W2008954381 @default.
- W2334607237 cites W2011358384 @default.
- W2334607237 cites W2012800025 @default.
- W2334607237 cites W2015553869 @default.
- W2334607237 cites W2019832290 @default.
- W2334607237 cites W2022128583 @default.
- W2334607237 cites W2024447680 @default.
- W2334607237 cites W2024811628 @default.
- W2334607237 cites W2026283109 @default.
- W2334607237 cites W2026653976 @default.
- W2334607237 cites W2027333770 @default.
- W2334607237 cites W2029076854 @default.
- W2334607237 cites W2034772825 @default.
- W2334607237 cites W2038246362 @default.
- W2334607237 cites W2039862840 @default.
- W2334607237 cites W2041901982 @default.
- W2334607237 cites W2044233393 @default.
- W2334607237 cites W2044490585 @default.
- W2334607237 cites W2045385945 @default.
- W2334607237 cites W2047940948 @default.
- W2334607237 cites W2049324079 @default.
- W2334607237 cites W2049907997 @default.
- W2334607237 cites W2051969855 @default.
- W2334607237 cites W2055214118 @default.
- W2334607237 cites W2055563809 @default.
- W2334607237 cites W2059050159 @default.
- W2334607237 cites W2059538067 @default.
- W2334607237 cites W2061668710 @default.
- W2334607237 cites W2062128824 @default.
- W2334607237 cites W2064532485 @default.
- W2334607237 cites W2068617439 @default.
- W2334607237 cites W2073002882 @default.
- W2334607237 cites W2073172981 @default.
- W2334607237 cites W2073513383 @default.
- W2334607237 cites W2076104173 @default.
- W2334607237 cites W2078146328 @default.
- W2334607237 cites W2082217729 @default.
- W2334607237 cites W2082656972 @default.
- W2334607237 cites W2084015885 @default.
- W2334607237 cites W2087606452 @default.
- W2334607237 cites W2089488673 @default.
- W2334607237 cites W2091843869 @default.
- W2334607237 cites W2092157292 @default.
- W2334607237 cites W2093851405 @default.
- W2334607237 cites W2096747776 @default.
- W2334607237 cites W2102455520 @default.
- W2334607237 cites W2103400998 @default.
- W2334607237 cites W2103477311 @default.
- W2334607237 cites W2104484273 @default.
- W2334607237 cites W2119292856 @default.
- W2334607237 cites W2126631340 @default.
- W2334607237 cites W2131580117 @default.
- W2334607237 cites W2132934971 @default.
- W2334607237 cites W2133918436 @default.
- W2334607237 cites W2135785928 @default.
- W2334607237 cites W2143981217 @default.
- W2334607237 cites W2145709112 @default.
- W2334607237 cites W2155133163 @default.
- W2334607237 cites W2161746465 @default.
- W2334607237 cites W2167373531 @default.
- W2334607237 cites W2319628733 @default.
- W2334607237 cites W2328185082 @default.
- W2334607237 cites W2949240035 @default.