Family of V(lll)-tristhiolato complexes relevant to functional models of vanadium nitrogenase: Synthesis and electronic structure investigations by means of high-frequency and -field electron paramagnetic resonance coupled to quantum chemical computations

Shengfa Ye, Frank Neese, Andrew Ozarowsk, Dmitry Smirnov, J. Krzystek, Joshua Telser, Ju Hsiou Liao, Chen Hsiung Hung, Wei Chen Chu, Yi Feng Tsai, Rong Chin Wang, Kun Yuan Chen, Hua Fen Hsu

Research output: Contribution to journalArticle

46 Citations (Scopus)

Abstract

A series of V(III) complexes of varying coordination number (5,6, and 7) all containing the PS3 ligand (PS3 = trianion of tris(2-thiophenyl)phosphine and its derivatives with other phenyl substituents) has been prepared and structurally characterized. The complexes have general formula [V(PS3)L n]0,-, where n= 1 (from L=Cl-, 1-Me-Im, N 3-), 2 (from L = 2,2'-bpy; counting each N of the bidentate ligand), and 3 (from L = 1-Me-Im, N2H4). The complexes have also been investigated by direct current (DC) magnetic susceptibility and high-frequency and -field electron paramagnetic resonance (HFEPR). HFEPR, supported by magnetometry, has provided accurate spin Hamiltonian parameters that describe the S= 1 spin ground state of the complexes. Of particular interest are the zero-field splitting (zfs) parameters which, together with structural data, are the empirical starting point for detailed computational studies. The computational methods included density functional theory (DFT), which was only marginally successful, and more advanced ab initio methods (CASSCF and SORCI). The zfs in these complexes is relatively small in magnitude (IDI ≈ 1cm-1) and is the result of multiple, often counteracting, spin-orbit coupling (SOC) and spin-spin coupling (SSC) contributions. The specific origin of each of these contributions is described in detail. The results indicate the level of electronic structure calculation possible for transition metal complexes even with multiple unpaired electrons and highly covalent, heavier atom donor ligands.

Original languageEnglish
Pages (from-to)977-988
Number of pages12
JournalInorganic Chemistry
Volume49
Issue number3
DOIs
Publication statusPublished - 2010 Feb 1

Fingerprint

Nitrogenase
vanadium
Electronic structure
Paramagnetic resonance
electron paramagnetic resonance
phosphine
Coordination Complexes
electronic structure
Ligands
ligands
synthesis
Hamiltonians
spin-spin coupling
Computational methods
Magnetic susceptibility
coordination number
phosphines
Ground state
magnetic measurement
Transition metals

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Ye, Shengfa ; Neese, Frank ; Ozarowsk, Andrew ; Smirnov, Dmitry ; Krzystek, J. ; Telser, Joshua ; Liao, Ju Hsiou ; Hung, Chen Hsiung ; Chu, Wei Chen ; Tsai, Yi Feng ; Wang, Rong Chin ; Chen, Kun Yuan ; Hsu, Hua Fen. / Family of V(lll)-tristhiolato complexes relevant to functional models of vanadium nitrogenase : Synthesis and electronic structure investigations by means of high-frequency and -field electron paramagnetic resonance coupled to quantum chemical computations. In: Inorganic Chemistry. 2010 ; Vol. 49, No. 3. pp. 977-988.
@article{6b92f87d26504beab3140adf6ed4252b,
title = "Family of V(lll)-tristhiolato complexes relevant to functional models of vanadium nitrogenase: Synthesis and electronic structure investigations by means of high-frequency and -field electron paramagnetic resonance coupled to quantum chemical computations",
abstract = "A series of V(III) complexes of varying coordination number (5,6, and 7) all containing the PS3 ligand (PS3 = trianion of tris(2-thiophenyl)phosphine and its derivatives with other phenyl substituents) has been prepared and structurally characterized. The complexes have general formula [V(PS3)L n]0,-, where n= 1 (from L=Cl-, 1-Me-Im, N 3-), 2 (from L = 2,2'-bpy; counting each N of the bidentate ligand), and 3 (from L = 1-Me-Im, N2H4). The complexes have also been investigated by direct current (DC) magnetic susceptibility and high-frequency and -field electron paramagnetic resonance (HFEPR). HFEPR, supported by magnetometry, has provided accurate spin Hamiltonian parameters that describe the S= 1 spin ground state of the complexes. Of particular interest are the zero-field splitting (zfs) parameters which, together with structural data, are the empirical starting point for detailed computational studies. The computational methods included density functional theory (DFT), which was only marginally successful, and more advanced ab initio methods (CASSCF and SORCI). The zfs in these complexes is relatively small in magnitude (IDI ≈ 1cm-1) and is the result of multiple, often counteracting, spin-orbit coupling (SOC) and spin-spin coupling (SSC) contributions. The specific origin of each of these contributions is described in detail. The results indicate the level of electronic structure calculation possible for transition metal complexes even with multiple unpaired electrons and highly covalent, heavier atom donor ligands.",
author = "Shengfa Ye and Frank Neese and Andrew Ozarowsk and Dmitry Smirnov and J. Krzystek and Joshua Telser and Liao, {Ju Hsiou} and Hung, {Chen Hsiung} and Chu, {Wei Chen} and Tsai, {Yi Feng} and Wang, {Rong Chin} and Chen, {Kun Yuan} and Hsu, {Hua Fen}",
year = "2010",
month = "2",
day = "1",
doi = "10.1021/ic9017745",
language = "English",
volume = "49",
pages = "977--988",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "3",

}

Family of V(lll)-tristhiolato complexes relevant to functional models of vanadium nitrogenase : Synthesis and electronic structure investigations by means of high-frequency and -field electron paramagnetic resonance coupled to quantum chemical computations. / Ye, Shengfa; Neese, Frank; Ozarowsk, Andrew; Smirnov, Dmitry; Krzystek, J.; Telser, Joshua; Liao, Ju Hsiou; Hung, Chen Hsiung; Chu, Wei Chen; Tsai, Yi Feng; Wang, Rong Chin; Chen, Kun Yuan; Hsu, Hua Fen.

In: Inorganic Chemistry, Vol. 49, No. 3, 01.02.2010, p. 977-988.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Family of V(lll)-tristhiolato complexes relevant to functional models of vanadium nitrogenase

T2 - Synthesis and electronic structure investigations by means of high-frequency and -field electron paramagnetic resonance coupled to quantum chemical computations

AU - Ye, Shengfa

AU - Neese, Frank

AU - Ozarowsk, Andrew

AU - Smirnov, Dmitry

AU - Krzystek, J.

AU - Telser, Joshua

AU - Liao, Ju Hsiou

AU - Hung, Chen Hsiung

AU - Chu, Wei Chen

AU - Tsai, Yi Feng

AU - Wang, Rong Chin

AU - Chen, Kun Yuan

AU - Hsu, Hua Fen

PY - 2010/2/1

Y1 - 2010/2/1

N2 - A series of V(III) complexes of varying coordination number (5,6, and 7) all containing the PS3 ligand (PS3 = trianion of tris(2-thiophenyl)phosphine and its derivatives with other phenyl substituents) has been prepared and structurally characterized. The complexes have general formula [V(PS3)L n]0,-, where n= 1 (from L=Cl-, 1-Me-Im, N 3-), 2 (from L = 2,2'-bpy; counting each N of the bidentate ligand), and 3 (from L = 1-Me-Im, N2H4). The complexes have also been investigated by direct current (DC) magnetic susceptibility and high-frequency and -field electron paramagnetic resonance (HFEPR). HFEPR, supported by magnetometry, has provided accurate spin Hamiltonian parameters that describe the S= 1 spin ground state of the complexes. Of particular interest are the zero-field splitting (zfs) parameters which, together with structural data, are the empirical starting point for detailed computational studies. The computational methods included density functional theory (DFT), which was only marginally successful, and more advanced ab initio methods (CASSCF and SORCI). The zfs in these complexes is relatively small in magnitude (IDI ≈ 1cm-1) and is the result of multiple, often counteracting, spin-orbit coupling (SOC) and spin-spin coupling (SSC) contributions. The specific origin of each of these contributions is described in detail. The results indicate the level of electronic structure calculation possible for transition metal complexes even with multiple unpaired electrons and highly covalent, heavier atom donor ligands.

AB - A series of V(III) complexes of varying coordination number (5,6, and 7) all containing the PS3 ligand (PS3 = trianion of tris(2-thiophenyl)phosphine and its derivatives with other phenyl substituents) has been prepared and structurally characterized. The complexes have general formula [V(PS3)L n]0,-, where n= 1 (from L=Cl-, 1-Me-Im, N 3-), 2 (from L = 2,2'-bpy; counting each N of the bidentate ligand), and 3 (from L = 1-Me-Im, N2H4). The complexes have also been investigated by direct current (DC) magnetic susceptibility and high-frequency and -field electron paramagnetic resonance (HFEPR). HFEPR, supported by magnetometry, has provided accurate spin Hamiltonian parameters that describe the S= 1 spin ground state of the complexes. Of particular interest are the zero-field splitting (zfs) parameters which, together with structural data, are the empirical starting point for detailed computational studies. The computational methods included density functional theory (DFT), which was only marginally successful, and more advanced ab initio methods (CASSCF and SORCI). The zfs in these complexes is relatively small in magnitude (IDI ≈ 1cm-1) and is the result of multiple, often counteracting, spin-orbit coupling (SOC) and spin-spin coupling (SSC) contributions. The specific origin of each of these contributions is described in detail. The results indicate the level of electronic structure calculation possible for transition metal complexes even with multiple unpaired electrons and highly covalent, heavier atom donor ligands.

UR - http://www.scopus.com/inward/record.url?scp=75649125273&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=75649125273&partnerID=8YFLogxK

U2 - 10.1021/ic9017745

DO - 10.1021/ic9017745

M3 - Article

C2 - 20028109

AN - SCOPUS:75649125273

VL - 49

SP - 977

EP - 988

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 3

ER -