Type 1 copper site synthetic model complexes with increased redox potentials

Lei Yang; William B. Tolman

doi:10.1007/s00775-011-0849-9

Type 1 copper site synthetic model complexes with increased redox potentials

Lei Yang, William B. Tolman

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

Abstract

Reactions of NaSCPh ₃ with (R ₃tacn)Cu(OTf) ₂ (R is Me, iPr; tacn is 1,4,7-triazacyclononane; OTf is CF ₃SO ₃ ^-) yield blue complexes identified as ((R ₃tacn) CuSCPh ₃)(OTf) on the basis of UV-vis, resonance Raman, and electron paramagnetic resonance (EPR) spectroscopy and electrospray ionization mass spectrometry. These complexes exhibit spectroscopic properties typical of type 1 copper sites in proteins, including diagnostic Sπ → Cu(d _x ²-y ²) ligand-to-metal charge transfer transitions at approximately 610-630 nm and small A _|| values in EPR spectra of less than 100 × 10 ^-4 cm ^-1. Cyclic voltammetry experiments revealed redox potentials for the complexes similar to those of several low-potential type 1 copper proteins (e.g., azurin, stellacyanin) and approximately 0.5 V higher than those of previously reported model compounds. Thus, the new complexes mimic key aspects of both the structure and the function of type 1 copper sites.

Original language	English (US)
Pages (from-to)	285-291
Number of pages	7
Journal	Journal of Biological Inorganic Chemistry
Volume	17
Issue number	2
DOIs	https://doi.org/10.1007/s00775-011-0849-9
State	Published - Feb 2012

Bibliographical note

Funding Information:
Acknowledgments We thank the NIH for financial support of this research (grant GM47365 to W.B.T.), Patrick Donoghue for assistance with EPR measurements, David Boyce for obtaining resonance Raman data, Jacqui Tehranchi for help with the electrochemistry experiments, and John Lipscomb and Lawrence Que Jr for access to EPR and resonance Raman facilities, respectively.

Keywords

Blue copper
Electrochemistry
Electron transfer
Spectroscopy
Type 1 copper

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10.1007/s00775-011-0849-9

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title = "Type 1 copper site synthetic model complexes with increased redox potentials",

abstract = "Reactions of NaSCPh 3 with (R 3tacn)Cu(OTf) 2 (R is Me, iPr; tacn is 1,4,7-triazacyclononane; OTf is CF 3SO 3 -) yield blue complexes identified as ((R 3tacn) CuSCPh 3)(OTf) on the basis of UV-vis, resonance Raman, and electron paramagnetic resonance (EPR) spectroscopy and electrospray ionization mass spectrometry. These complexes exhibit spectroscopic properties typical of type 1 copper sites in proteins, including diagnostic Sπ → Cu(d x 2-y 2) ligand-to-metal charge transfer transitions at approximately 610-630 nm and small A || values in EPR spectra of less than 100 × 10 -4 cm -1. Cyclic voltammetry experiments revealed redox potentials for the complexes similar to those of several low-potential type 1 copper proteins (e.g., azurin, stellacyanin) and approximately 0.5 V higher than those of previously reported model compounds. Thus, the new complexes mimic key aspects of both the structure and the function of type 1 copper sites.",

keywords = "Blue copper, Electrochemistry, Electron transfer, Spectroscopy, Type 1 copper",

author = "Lei Yang and Tolman, {William B.}",

note = "Funding Information: Acknowledgments We thank the NIH for financial support of this research (grant GM47365 to W.B.T.), Patrick Donoghue for assistance with EPR measurements, David Boyce for obtaining resonance Raman data, Jacqui Tehranchi for help with the electrochemistry experiments, and John Lipscomb and Lawrence Que Jr for access to EPR and resonance Raman facilities, respectively.",

year = "2012",

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doi = "10.1007/s00775-011-0849-9",

language = "English (US)",

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TY - JOUR

T1 - Type 1 copper site synthetic model complexes with increased redox potentials

AU - Yang, Lei

AU - Tolman, William B.

N1 - Funding Information: Acknowledgments We thank the NIH for financial support of this research (grant GM47365 to W.B.T.), Patrick Donoghue for assistance with EPR measurements, David Boyce for obtaining resonance Raman data, Jacqui Tehranchi for help with the electrochemistry experiments, and John Lipscomb and Lawrence Que Jr for access to EPR and resonance Raman facilities, respectively.

PY - 2012/2

Y1 - 2012/2

N2 - Reactions of NaSCPh 3 with (R 3tacn)Cu(OTf) 2 (R is Me, iPr; tacn is 1,4,7-triazacyclononane; OTf is CF 3SO 3 -) yield blue complexes identified as ((R 3tacn) CuSCPh 3)(OTf) on the basis of UV-vis, resonance Raman, and electron paramagnetic resonance (EPR) spectroscopy and electrospray ionization mass spectrometry. These complexes exhibit spectroscopic properties typical of type 1 copper sites in proteins, including diagnostic Sπ → Cu(d x 2-y 2) ligand-to-metal charge transfer transitions at approximately 610-630 nm and small A || values in EPR spectra of less than 100 × 10 -4 cm -1. Cyclic voltammetry experiments revealed redox potentials for the complexes similar to those of several low-potential type 1 copper proteins (e.g., azurin, stellacyanin) and approximately 0.5 V higher than those of previously reported model compounds. Thus, the new complexes mimic key aspects of both the structure and the function of type 1 copper sites.

AB - Reactions of NaSCPh 3 with (R 3tacn)Cu(OTf) 2 (R is Me, iPr; tacn is 1,4,7-triazacyclononane; OTf is CF 3SO 3 -) yield blue complexes identified as ((R 3tacn) CuSCPh 3)(OTf) on the basis of UV-vis, resonance Raman, and electron paramagnetic resonance (EPR) spectroscopy and electrospray ionization mass spectrometry. These complexes exhibit spectroscopic properties typical of type 1 copper sites in proteins, including diagnostic Sπ → Cu(d x 2-y 2) ligand-to-metal charge transfer transitions at approximately 610-630 nm and small A || values in EPR spectra of less than 100 × 10 -4 cm -1. Cyclic voltammetry experiments revealed redox potentials for the complexes similar to those of several low-potential type 1 copper proteins (e.g., azurin, stellacyanin) and approximately 0.5 V higher than those of previously reported model compounds. Thus, the new complexes mimic key aspects of both the structure and the function of type 1 copper sites.

KW - Blue copper

KW - Electrochemistry

KW - Electron transfer

KW - Spectroscopy

KW - Type 1 copper

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Type 1 copper site synthetic model complexes with increased redox potentials

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