TY - JOUR
T1 - Syntheses and Characterization of Two Dioxygen Reactive Dinuclear Macrocyclic Schiff-base Copper(I) Complexes
AU - Utz, D
AU - Heinemann, FW
AU - Hampel, F
AU - Richens, David Trevor
AU - Schindler, S
PY - 2003/3/10
Y1 - 2003/3/10
N2 - The dinuclear copper(I) complex [Cu2L1(CH3CN)(2)](ClO4)(2) (1, L-1 = 3,6,9,17,20,23-hexaazatricyclo[23.3.1.1]triaconta-1(29),2,9,11(30),12(13),14,16,23,25,27-decaene) has been structurally characterized. As previously described, intramolecular ligand hydroxylation (at the aromatic ring) was observed when 1 was reacted with dioxygen. A stopped-flow analysis of the reaction of 1 With dioxygen under different conditions did not allow a "dioxygen intermediate" to be spectroscopically detected. Detailed NMR and electrochemical data on 1 are also presented and evaluated for the first time. No copper(II) complexes of L-1 could be characterized due to hydrolysis of the compounds. In contrast, complex 2-differing from 1 only in an increase in the size of the chelate rings-did not undergo intramolecular hydroxylation when it was oxidized. The crystal structure of 2 is also described.
AB - The dinuclear copper(I) complex [Cu2L1(CH3CN)(2)](ClO4)(2) (1, L-1 = 3,6,9,17,20,23-hexaazatricyclo[23.3.1.1]triaconta-1(29),2,9,11(30),12(13),14,16,23,25,27-decaene) has been structurally characterized. As previously described, intramolecular ligand hydroxylation (at the aromatic ring) was observed when 1 was reacted with dioxygen. A stopped-flow analysis of the reaction of 1 With dioxygen under different conditions did not allow a "dioxygen intermediate" to be spectroscopically detected. Detailed NMR and electrochemical data on 1 are also presented and evaluated for the first time. No copper(II) complexes of L-1 could be characterized due to hydrolysis of the compounds. In contrast, complex 2-differing from 1 only in an increase in the size of the chelate rings-did not undergo intramolecular hydroxylation when it was oxidized. The crystal structure of 2 is also described.
KW - C-H BOND
KW - INTRAMOLECULAR LIGAND HYDROXYLATION
KW - MONOOXYGENASE MODEL SYSTEM
KW - RAY CRYSTAL-STRUCTURE
KW - OXYGEN INSERTION
KW - BINUCLEATING LIGANDS
KW - DICOPPER COMPLEXES
KW - METAL-COMPLEXES
KW - HIGH-PRESSURE
KW - TYROSINASE
UR - http://www.scopus.com/inward/record.url?scp=0037430171&partnerID=8YFLogxK
UR - http://pubs.acs.org/cgi-bin/article.cgi/inocaj/2003/42/i05/pdf/ic025731+.pdf
U2 - 10.1021/ic025731+
DO - 10.1021/ic025731+
M3 - Article
SN - 0020-1669
VL - 42
SP - 1430
EP - 1436
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 5
ER -