TY - JOUR
T1 - Electrochemical and spectroelectrochemical investigation of Ru(por)(NO)(OAr) derivatives (por = octaethylporphyrin, tetraanisolylporphyrin; Ar = Ph, C6H4-2-NHC( 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 O)CF3; C6H3-2,6-(NHC( O)CF3)2)
AU - Ramuglia, Anthony R.
AU - Zink, Jeremy R.
AU - Warhausen, Adam J.
AU - Abucayon, Erwin
AU - Xu, Nan
AU - Shrestha, Kailash
AU - Richter-Addo, George
AU - Shaw, Michael J.
N1 - Publisher Copyright:
© 2025 The Royal Society of Chemistry.
PY - 2025/1/22
Y1 - 2025/1/22
N2 - The electrochemistry and spectroelectrochemistry of Ru(porphyrin)(NO)(phenoxide) complexes Ru(por)(NO)(OPh) (por = OEP, 1a; TAP, 2a; Ph = C6H5), Ru(por)(NO)(OAr1) (por = OEP, 1b; TAP, 2b; OAr1 = -OC6H4-(2-NHC( O)CF3)), Ru(por)(NO)(OAr2) (por = OEP, 1c; TAP, 2c; OAr2 = OC6H3-(2,6-NHC( O)CF3)2; OEP = octaethylporphyrinato dianion, TAP = tetraanisolylporphyrinato dianion) indicate that initial one-electron oxidation results in structure-dependent net reactivity at the phenoxide ligand. Oxidation of 1a generates 1a+, which undergoes a relatively slow rate-limiting second-order follow-up reaction. In contrast, 2a undergoes a diffusion-limited follow-up reaction after oxidation. Oxidation of species 1b and 2b results in dissociation of the corresponding phenoxide radicals from the metal center following a relatively slow first-order kinetic process. The ˙OAr1 radical was detected by EPR spectroelectrochemistry. The follow-up reactions after oxidation of 1c and 2c are also very fast. In all cases, the ultimate fate of the ruthenium complex is to be trapped with adventitious water to generate the stable aqua complex. Further oxidation of each compound at higher potentials occurs at the porphyrin ligand, generating the π-radical cation observed by IR spectroelectrochemistry.
AB - The electrochemistry and spectroelectrochemistry of Ru(porphyrin)(NO)(phenoxide) complexes Ru(por)(NO)(OPh) (por = OEP, 1a; TAP, 2a; Ph = C6H5), Ru(por)(NO)(OAr1) (por = OEP, 1b; TAP, 2b; OAr1 = -OC6H4-(2-NHC( O)CF3)), Ru(por)(NO)(OAr2) (por = OEP, 1c; TAP, 2c; OAr2 = OC6H3-(2,6-NHC( O)CF3)2; OEP = octaethylporphyrinato dianion, TAP = tetraanisolylporphyrinato dianion) indicate that initial one-electron oxidation results in structure-dependent net reactivity at the phenoxide ligand. Oxidation of 1a generates 1a+, which undergoes a relatively slow rate-limiting second-order follow-up reaction. In contrast, 2a undergoes a diffusion-limited follow-up reaction after oxidation. Oxidation of species 1b and 2b results in dissociation of the corresponding phenoxide radicals from the metal center following a relatively slow first-order kinetic process. The ˙OAr1 radical was detected by EPR spectroelectrochemistry. The follow-up reactions after oxidation of 1c and 2c are also very fast. In all cases, the ultimate fate of the ruthenium complex is to be trapped with adventitious water to generate the stable aqua complex. Further oxidation of each compound at higher potentials occurs at the porphyrin ligand, generating the π-radical cation observed by IR spectroelectrochemistry.
UR - https://www.scopus.com/pages/publications/85216391819
UR - https://www.scopus.com/pages/publications/85216391819#tab=citedBy
U2 - 10.1039/d4dt02764g
DO - 10.1039/d4dt02764g
M3 - Article
C2 - 39844611
AN - SCOPUS:85216391819
SN - 1477-9226
VL - 54
SP - 3444
EP - 3455
JO - Dalton Transactions
JF - Dalton Transactions
IS - 8
ER -