Zhou L, Powell D, Nicholas K M
Department of Chemistry and Biochemistry, University of Oklahoma, Norman, Oklahoma 73019, USA.
Inorg Chem. 2006 May 15;45(10):3840-2. doi: 10.1021/ic052121b.
Tripodal bis(imidazole) thioether ligands and the corresponding copper(I) complexes [(BIMT-OR)Cu(L)]PF6 [L = CH3CN (2), CO (3); R = H (a), CH3 (b)] have been prepared as models for the Cu(B) site of copper hydroxylase enzymes. The IR (CO) values of 3a and 3b (L = CO) are comparable to those of the carbonylated enzymes. The reaction of 2a with O2 gives dinuclear complex 4 with bridging BIMT-O ligands and oxidized -SMe groups, whereas oxygenation of 2b affords (BIMT-OMe)2Cu2O(H)22 (5) and Cu(BIMT-OMe)(DMF)2](PF6)2 (6).
三脚架双(咪唑)硫醚配体及相应的铜(I)配合物[(BIMT-OR)Cu(L)]PF6 [L = CH3CN(2),CO(3);R = H(a),CH3(b)]已被制备作为铜羟化酶中Cu(B)位点的模型。3a和3b(L = CO)的红外(CO)值与羰基化酶的红外值相当。2a与O2反应生成具有桥联BIMT-O配体和氧化-SMe基团的双核配合物4,而2b的氧化则得到(BIMT-OMe)2Cu2O(H)22(5)和Cu(BIMT-OMe)(DMF)22(6)。