Family of V(III)-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; Ozarowski, 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

doi:10.1021/ic9017745

アイテム詳細

登録内容を編集ファイル形式で保存

一時保存へ追加

タグ情報を表示リリース履歴を表示詳細要約

公開

学術論文

Family of V(III)-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

MPS-Authors

There are no MPG-Authors in the publication available

External Resource

There are no locators available

Fulltext (restricted access)

There are currently no full texts shared for your IP range.

フルテキスト (公開)

公開されているフルテキストはありません

付随資料 (公開)

There is no public supplementary material available

引用

Ye, S., Neese, F., Ozarowski, A., Smirnov, D., Krzystek, J., Telser, J., Liao, J.-H., Hung, C.-H., Chu, W.-C., Tsai, Y.-F., Wang, R.-C., Chen, K.-Y., & Hsu, H.-F. (2010). Family of V(III)-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. Inorganic Chemistry, 49(3), 977-988. doi:10.1021/ic9017745.

引用: https://hdl.handle.net/21.11116/0000-0008-101F-4

要旨

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, N₃⁻), 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 (|D| ≈ 1 cm⁻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.