TY - JOUR
T1 - Coupling of nitric oxide and release of nitrous oxide from rare-earth-dinitrosyliron complexes
AU - Bar, Arun Kumar
AU - Heras Ojea, María José
AU - Tang, Jinkui
AU - Layfield, Richard A.
N1 - Copyright © 2020 American Chemical Society
Arun Kumar Bar, María José Heras Ojea, Jinkui Tang, and Richard A. Layfield Journal of the American Chemical Society 2020 142 (9), 4104-4107 DOI: 10.1021/jacs.9b13571
PY - 2020/3/4
Y1 - 2020/3/4
N2 - Addition of Lewis acidic [Cp*2M]+ (M = Y, Gd) to the dinitrosyliron complexes (DNICs) [(NacNacAr)Fe(NO)2]− (Ar = mesityl, 2,6-diisopropylphenyl) results in formation of the isonitrosyl-bridged DNICs [(Cp*)2M(μ-ON)2Fe(NacNacAr)]. When Ar = 2,6-diisopropylphenyl, coupling of the NO ligands and release of N2O occur. Two factors contribute to this previously unobserved DNIC reactivity mode. First, the oxophilic rare-earth elements drive the formation of isonitrosyl bonds, forcing the DNIC nitrogen atoms into proximity. Second, the bulky substituents further squeeze the DNIC, which ultimately overcomes the barrier to NO coupling, demonstrating that N2O elimination can occur from a single iron center.
AB - Addition of Lewis acidic [Cp*2M]+ (M = Y, Gd) to the dinitrosyliron complexes (DNICs) [(NacNacAr)Fe(NO)2]− (Ar = mesityl, 2,6-diisopropylphenyl) results in formation of the isonitrosyl-bridged DNICs [(Cp*)2M(μ-ON)2Fe(NacNacAr)]. When Ar = 2,6-diisopropylphenyl, coupling of the NO ligands and release of N2O occur. Two factors contribute to this previously unobserved DNIC reactivity mode. First, the oxophilic rare-earth elements drive the formation of isonitrosyl bonds, forcing the DNIC nitrogen atoms into proximity. Second, the bulky substituents further squeeze the DNIC, which ultimately overcomes the barrier to NO coupling, demonstrating that N2O elimination can occur from a single iron center.
KW - NO ligands
KW - dinitrosyliron complexes
KW - oxophilic rare-earth elements
KW - cardiovascular system
KW - nitric oxide
KW - nitrous oxide
U2 - 10.1021/jacs.9b13571
DO - 10.1021/jacs.9b13571
M3 - Article
SN - 0002-7863
VL - 142
SP - 4104
EP - 4107
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 9
ER -