Single-Crystal, Solid-State, and Solution 113Cd NMR Studies of [Cd(SR)2(N-donor)2] Complexes. Structural and Spectroscopic Analogues for Biologically Occurring [M(iS-Cys)2(His)2] Centers

Rodolfo A. Santos, Eric S. Gruff, Stephen A. Koch, Gerard S. Harbison

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Abstract

A series of compounds of the formula [Cd(SR)2(N-donor)2] has been synthesized, characterized by X-ray crystallography, and studied by solid-state and solution 113Cd NMR spectroscopy to serve as analogues for biologically occurring [M(5-Cys)2(His)2] centers. The compounds include [Cd(S-2,4,6-(-Pr3-C6H2)2(bpy)] (1), [Cd(S-2,4,6-i-Pr3-C6H2)2(phen)]2 (2), [Cd(S-2,4,6-i-Pr3-C6H2)2(1-Me-imid)2] (3), and [Cd(S-2,4,6-i-Pr3-C6H2)2(1,2-Me2-imid)2] (4). Compounds 1-3 have been characterized by X-ray crystallography. The unit cell parameters are as follows. For I: a = 15.081 (9)Å, b = 14.716 (9) Å, c = 17.72 (1) Å, β = 100.36 (5)°, V= 3868 (8) Å3, Z = 4, P21/c. For 2: a = 10.12 (2) Å, b = 16.56 (1) Å, c = 23.50 (2) Å, β = 92.1 (5)°, V = 3934 (14) Å3, Z = 2, P21/n. For 3: a = 16.541 (7) Å, b = 15.887 (6) Å, c = 16.36 (1) Å, β = 108.91 (5)°, V = 4068 (7) Å3, Z = 4, P21/c. Compounds 1-4 have been characterized by solution and CP/MAS 113Cd spectroscopy. The 13Cd shielding tensors of 1 have been obtained from a single-crystal study (σ11 = 814 σ22 = 630 ppm, σ33 = 32 ppm). Similar large chemical shielding anisotropies (CSA) were also observed for 2-4. The solution 113Cd NMR spectra arc consistent with monomeric [Cd(SR)2(N)2] structures. The large difference in the 113Cd chemical shift for 2 in the solution and solid state is explained by the weak dimeric structure of 2 in the solid state. The implications of the large CSA to solution and solid-state measurements of related centers in proteins are discussed.

Original languageEnglish (US)
Pages (from-to)9257-9263
Number of pages7
JournalJournal of the American Chemical Society
Volume112
Issue number25
DOIs
StatePublished - Jan 1990

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Nuclear magnetic resonance
Single crystals
Shielding
X ray crystallography
X Ray Crystallography
Anisotropy
Chemical shift
Nuclear magnetic resonance spectroscopy
Tensors
Spectrum Analysis
Magnetic Resonance Spectroscopy
Spectroscopy
Proteins

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

@article{5a6a8f938fb043f698e2383c75fc6fe7,
title = "Single-Crystal, Solid-State, and Solution 113Cd NMR Studies of [Cd(SR)2(N-donor)2] Complexes. Structural and Spectroscopic Analogues for Biologically Occurring [M(iS-Cys)2(His)2] Centers",
abstract = "A series of compounds of the formula [Cd(SR)2(N-donor)2] has been synthesized, characterized by X-ray crystallography, and studied by solid-state and solution 113Cd NMR spectroscopy to serve as analogues for biologically occurring [M(5-Cys)2(His)2] centers. The compounds include [Cd(S-2,4,6-(-Pr3-C6H2)2(bpy)] (1), [Cd(S-2,4,6-i-Pr3-C6H2)2(phen)]2 (2), [Cd(S-2,4,6-i-Pr3-C6H2)2(1-Me-imid)2] (3), and [Cd(S-2,4,6-i-Pr3-C6H2)2(1,2-Me2-imid)2] (4). Compounds 1-3 have been characterized by X-ray crystallography. The unit cell parameters are as follows. For I: a = 15.081 (9){\AA}, b = 14.716 (9) {\AA}, c = 17.72 (1) {\AA}, β = 100.36 (5)°, V= 3868 (8) {\AA}3, Z = 4, P21/c. For 2: a = 10.12 (2) {\AA}, b = 16.56 (1) {\AA}, c = 23.50 (2) {\AA}, β = 92.1 (5)°, V = 3934 (14) {\AA}3, Z = 2, P21/n. For 3: a = 16.541 (7) {\AA}, b = 15.887 (6) {\AA}, c = 16.36 (1) {\AA}, β = 108.91 (5)°, V = 4068 (7) {\AA}3, Z = 4, P21/c. Compounds 1-4 have been characterized by solution and CP/MAS 113Cd spectroscopy. The 13Cd shielding tensors of 1 have been obtained from a single-crystal study (σ11 = 814 σ22 = 630 ppm, σ33 = 32 ppm). Similar large chemical shielding anisotropies (CSA) were also observed for 2-4. The solution 113Cd NMR spectra arc consistent with monomeric [Cd(SR)2(N)2] structures. The large difference in the 113Cd chemical shift for 2 in the solution and solid state is explained by the weak dimeric structure of 2 in the solid state. The implications of the large CSA to solution and solid-state measurements of related centers in proteins are discussed.",
author = "Santos, {Rodolfo A.} and Gruff, {Eric S.} and Koch, {Stephen A.} and Harbison, {Gerard S.}",
year = "1990",
month = "1",
doi = "10.1021/ja00181a031",
language = "English (US)",
volume = "112",
pages = "9257--9263",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "25",

}

TY - JOUR

T1 - Single-Crystal, Solid-State, and Solution 113Cd NMR Studies of [Cd(SR)2(N-donor)2] Complexes. Structural and Spectroscopic Analogues for Biologically Occurring [M(iS-Cys)2(His)2] Centers

AU - Santos, Rodolfo A.

AU - Gruff, Eric S.

AU - Koch, Stephen A.

AU - Harbison, Gerard S.

PY - 1990/1

Y1 - 1990/1

N2 - A series of compounds of the formula [Cd(SR)2(N-donor)2] has been synthesized, characterized by X-ray crystallography, and studied by solid-state and solution 113Cd NMR spectroscopy to serve as analogues for biologically occurring [M(5-Cys)2(His)2] centers. The compounds include [Cd(S-2,4,6-(-Pr3-C6H2)2(bpy)] (1), [Cd(S-2,4,6-i-Pr3-C6H2)2(phen)]2 (2), [Cd(S-2,4,6-i-Pr3-C6H2)2(1-Me-imid)2] (3), and [Cd(S-2,4,6-i-Pr3-C6H2)2(1,2-Me2-imid)2] (4). Compounds 1-3 have been characterized by X-ray crystallography. The unit cell parameters are as follows. For I: a = 15.081 (9)Å, b = 14.716 (9) Å, c = 17.72 (1) Å, β = 100.36 (5)°, V= 3868 (8) Å3, Z = 4, P21/c. For 2: a = 10.12 (2) Å, b = 16.56 (1) Å, c = 23.50 (2) Å, β = 92.1 (5)°, V = 3934 (14) Å3, Z = 2, P21/n. For 3: a = 16.541 (7) Å, b = 15.887 (6) Å, c = 16.36 (1) Å, β = 108.91 (5)°, V = 4068 (7) Å3, Z = 4, P21/c. Compounds 1-4 have been characterized by solution and CP/MAS 113Cd spectroscopy. The 13Cd shielding tensors of 1 have been obtained from a single-crystal study (σ11 = 814 σ22 = 630 ppm, σ33 = 32 ppm). Similar large chemical shielding anisotropies (CSA) were also observed for 2-4. The solution 113Cd NMR spectra arc consistent with monomeric [Cd(SR)2(N)2] structures. The large difference in the 113Cd chemical shift for 2 in the solution and solid state is explained by the weak dimeric structure of 2 in the solid state. The implications of the large CSA to solution and solid-state measurements of related centers in proteins are discussed.

AB - A series of compounds of the formula [Cd(SR)2(N-donor)2] has been synthesized, characterized by X-ray crystallography, and studied by solid-state and solution 113Cd NMR spectroscopy to serve as analogues for biologically occurring [M(5-Cys)2(His)2] centers. The compounds include [Cd(S-2,4,6-(-Pr3-C6H2)2(bpy)] (1), [Cd(S-2,4,6-i-Pr3-C6H2)2(phen)]2 (2), [Cd(S-2,4,6-i-Pr3-C6H2)2(1-Me-imid)2] (3), and [Cd(S-2,4,6-i-Pr3-C6H2)2(1,2-Me2-imid)2] (4). Compounds 1-3 have been characterized by X-ray crystallography. The unit cell parameters are as follows. For I: a = 15.081 (9)Å, b = 14.716 (9) Å, c = 17.72 (1) Å, β = 100.36 (5)°, V= 3868 (8) Å3, Z = 4, P21/c. For 2: a = 10.12 (2) Å, b = 16.56 (1) Å, c = 23.50 (2) Å, β = 92.1 (5)°, V = 3934 (14) Å3, Z = 2, P21/n. For 3: a = 16.541 (7) Å, b = 15.887 (6) Å, c = 16.36 (1) Å, β = 108.91 (5)°, V = 4068 (7) Å3, Z = 4, P21/c. Compounds 1-4 have been characterized by solution and CP/MAS 113Cd spectroscopy. The 13Cd shielding tensors of 1 have been obtained from a single-crystal study (σ11 = 814 σ22 = 630 ppm, σ33 = 32 ppm). Similar large chemical shielding anisotropies (CSA) were also observed for 2-4. The solution 113Cd NMR spectra arc consistent with monomeric [Cd(SR)2(N)2] structures. The large difference in the 113Cd chemical shift for 2 in the solution and solid state is explained by the weak dimeric structure of 2 in the solid state. The implications of the large CSA to solution and solid-state measurements of related centers in proteins are discussed.

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