Hydrotris(triazolyl)borate complexes as functional models for Cu nitrite reductase: the electronic influence of distal nitrogens.
Hydrotris(triazolyl)borate (Ttz) ligands form CuNO(x) (x = 2, 3) complexes for structural and functional models of copper nitrite reductase. These complexes have distinct properties relative to complexes of hydrotris(pyrazolyl)borate (Tp) and neutral tridentate N-donor ligands. The electron paramagnetic resonance spectra of five-coordinate copper complexes show rare nitrogen superhyperfine couplings with the Ttz ligand, indicating strong σ donation. The copper(I) nitrite complex [PPN](+)[(Ttz(tBu,Me))Cu(I)NO(2)](-) has been synthesized and characterized and allows for the stoichiometric reduction of NO(2)(-) to NO with H(+) addition. Anionic Cu(I) nitrite complexes are unusual and are stabilized here for the first time because Ttz is a good π acceptor.
Department of Chemistry, Drexel University, 3141 Chestnut Street, Philadelphia, Pennsylvania 19104, United States.
Mukesh
M
Kumar
Natalie A
NA
Dixon
Anna C
AC
Merkle
Matthias
M
Zeller
Nicolai
N
Lehnert
Elizabeth T
ET
Papish
D001881:Borates / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy; D004583:Electrons; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009572:Nitrite Reductases / Q000737:chemistry / Q000378:metabolism*; D009584:Nitrogen / Q000737:chemistry / Q000378:metabolism*; D009942:Organometallic Compounds / Q000737:chemistry / Q000378:metabolism*
D001881:Borates; D008024:Ligands; D009942:Organometallic Compounds; D003300:Copper; D009572:Nitrite Reductases; C052695:nitrite reductase, copper-containing; D009584:Nitrogen