Correlation of the Electronic and Geometric Structures in Mononuclear Copper(II) Superoxide Complexes

被引：40

作者：

Ginsbach, Jake W. ^{[1
]}

Peterson, Ryan L. ^{[2
]}

Cowley, Ryan E. ^{[1
]}

Karlin, Kenneth D. ^{[2
]}

Solomon, Edward I. ^{[1
]}

机构：

[1] Stanford Univ, Dept Chem, Stanford, CA 94305 USA

[2] Johns Hopkins Univ, Dept Chem, Baltimore, MD 21218 USA

来源：

INORGANIC CHEMISTRY | 2013年 / 52卷 / 22期

关键词：

END-ON; DIOXYGEN ADDUCT; CU-II; MONOOXYGENASE; ACTIVATION;

D O I：

10.1021/ic402357u

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The geometry of mononuclear copper(II) superoxide complexes has been shown to determine their ground state where side-on bonding leads to a singlet ground state and end-on complexes have triplet ground states. In an apparent contrast to this trend, the recently synthesized (HIPT(3)tren)(CuO2 center dot-)-O-II (1) was proposed to have an end-on geometry and a singlet ground state. However, reexamination of 1 with resonance Raman, magnetic circular dichroism, and H-2 NMR spectroscopies indicate that 1 is, in fact, an end-on superoxide species with a triplet ground state that results from the single (CuO2 center dot-)-O-II bonding interaction being weaker than the spin-pairing energy.

引用

页码：12872 / 12874

页数：3

共 14 条

[1] Spectroscopic and electronic structure studies of the diamagnetic side-on CuII-superoxo complex Cu(O2)[HB(3-R-5-iPrpz)3]:: Antiferromagnetic coupling versus covalent delocalization
Chen, P
Root, DE
Campochiaro, C
Fujisawa, K
Solomon, EI
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (02) : 466 - 474
[2] Oxygen activation by the noncoupled binuclear copper site in peptidylglycine α-hydroxylating monooxygenase.: Spectroscopic definition of the resting sites and the putative CuIIM-OOH intermediate
Chen, P
Bell, J
Eipper, BA
Solomon, EI
[J]. BIOCHEMISTRY, 2004, 43 (19) : 5735 - 5747
[3] Evidence that dioxygen and substrate activation are tightly coupled in dopamine β-monooxygenase -: Implications for the reactive oxygen species
Evans, JP
Ahn, K
Klinman, JP
[J]. JOURNAL OF BIOLOGICAL CHEMISTRY, 2003, 278 (50) : 49691 - 49698
[4] A MONOMERIC SIDE-ON SUPEROXOCOPPER(II) COMPLEX - CU(O-2)(HB(3-TBU-5-IPRPZ)(3))
FUJISAWA, K
TANAKA, M
MOROOKA, Y
KITAJIMA, N
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (26) : 12079 - 12080
[5] Copper(I)-Dioxygen Reactivity in a Sterically Demanding Tripodal Tetradentate tren Ligand: Formation and Reactivity of a Mononuclear Copper(II) End-On Superoxo Complex
Kobayashi, Yuki
Ohkubo, Kei
Nomura, Takashi
Kubo, Minoru
Fujieda, Nobutaka
Sugimoto, Hideki
Fukuzumi, Shunichi
Goto, Kei
Ogura, Takashi
Itoh, Shinobu
[J]. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2012, (29) : 4574 - 4578
[6] SOLUBILITY OF OXYGEN AND NITROGEN IN ORGANIC SOLVENTS FROM -25-DEGREES-C TO 50-DEGREES-C
KRETSCHMER, CB
NOWAKOWSKA, J
WIEBE, R
[J]. INDUSTRIAL AND ENGINEERING CHEMISTRY, 1946, 38 (05): : 506 - 509
[7] Oxygen isotope effects upon reversible O2-binding reactions:: Characterizing mononuclear superoxide and peroxide structures
Lanci, Michael P.
Roth, Justine P.
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (50) : 16006 - 16007
[8] A 1:1 copper-dioxygen adduct is an end-on bound superoxo copper(II) complex which undergoes oxygenation reactions with phenols
Maiti, Debabrata
Fry, H. Christopher
Woertink, Julia S.
Vance, Michael A.
Solomon, Edward I.
Karlin, Kenneth D.
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (02) : 264 - 265
[9] Cellobiose Dehydrogenase and a Copper-Dependent Polysaccharide Monooxygenase Potentiate Cellulose Degradation by Neurospora crassa
Phillips, Christopher M.
Beeson, William T.
Cate, Jamie H.
Marletta, Michael A.
[J]. ACS CHEMICAL BIOLOGY, 2011, 6 (12) : 1399 - 1406
[10] Dioxygen binds end-on to mononuclear copper in a precatalytic enzyme complex
Prigge, ST
Eipper, BA
Mains, RE
Amzel, LM
[J]. SCIENCE, 2004, 304 (5672) : 864 - 867

← 1 2 →