Ligand-Based Reactivity of Oxygenation and Alkylation in Cobalt Complexes Binding with (Thiolato)phosphine Derivatives

Yi Ying Wu; Jia Cheng Hong; Ruei Fong Tsai; Hung Ruei Pan; Bo Hua Huang; Yun Wei Chiang; Gene Hsiang Lee; Mu Jeng Cheng; Hua Fen Hsu

doi:10.1021/acs.inorgchem.9b03740

Ligand-Based Reactivity of Oxygenation and Alkylation in Cobalt Complexes Binding with (Thiolato)phosphine Derivatives

Yi Ying Wu, Jia Cheng Hong, Ruei Fong Tsai, Hung Ruei Pan, Bo Hua Huang, Yun Wei Chiang, Gene Hsiang Lee, Mu Jeng Cheng, Hua Fen Hsu

Department of Chemistry

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

6 Citations (Scopus)

Abstract

In our efforts to understand the nature of metal thiolates, we have explored the chemistry of cobalt ion supported by (thiolato)phosphine ligand derivatives. Herein, we synthesized and characterized a square-planar Co^II complex binding with a bidentate (thiolato)phosphine ligand, Co(PS1″)₂ (1) ([PS1″]^- = [P(Ph)₂(C₆H₃-3-SiMe₃-2-S)]^-). The complex activates O₂ to form a ligand-based oxygenation product, Co(OPS1″)₂ (2) ([OPS1″]^- = [PO(Ph)₂(C₆H₃-3-SiMe₃-2-S)]^-). In addition, an octahedral Co^III complex with a tridentate bis(thiolato)phosphine ligand, [NEt₄][Co(PS2*)₂] (3) ([PS2*]^2- = [P(Ph)(C₆H₃-3-Ph-2-S)₂]^2-), was obtained. Compound 3 cleaves the C-Cl bond in dichloromethane via an S-based nucleophilic attack to generate a chloromethyl thioether group. Two isomeric products, [Co(PS2*)(PSS^CH₂Cl*)] (4 and 4′) ([PSS^CH₂Cl*]^- = [P(Ph)(C₆H₃-3-Ph-2-S)(C₆H₃-3-Ph-2-SCH₂Cl)]^-), were isolated and fully characterized. Both transformations, oxygenation of a Co^II-bound phosphine donor in 1 and alkylation of a Co^III-bound thiolate in 3, were monitored by spectroscopic methods. These reaction products were isolated and fully characterized. Density functional theory (DFT, the B3LYP functional) calculations were performed to understand the electronic structure of 1 as well as the pathway of its transformation to 2.

Original language	English
Pages (from-to)	4650-4660
Number of pages	11
Journal	Inorganic Chemistry
Volume	59
Issue number	7
DOIs	https://doi.org/10.1021/acs.inorgchem.9b03740
Publication status	Published - 2020 Apr 6

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

Access to Document

10.1021/acs.inorgchem.9b03740

Cite this

@article{ae8ab6fcbac949a5996537ff9165eb4d,

title = "Ligand-Based Reactivity of Oxygenation and Alkylation in Cobalt Complexes Binding with (Thiolato)phosphine Derivatives",

abstract = "In our efforts to understand the nature of metal thiolates, we have explored the chemistry of cobalt ion supported by (thiolato)phosphine ligand derivatives. Herein, we synthesized and characterized a square-planar CoII complex binding with a bidentate (thiolato)phosphine ligand, Co(PS1″)2 (1) ([PS1″]- = [P(Ph)2(C6H3-3-SiMe3-2-S)]-). The complex activates O2 to form a ligand-based oxygenation product, Co(OPS1″)2 (2) ([OPS1″]- = [PO(Ph)2(C6H3-3-SiMe3-2-S)]-). In addition, an octahedral CoIII complex with a tridentate bis(thiolato)phosphine ligand, [NEt4][Co(PS2*)2] (3) ([PS2*]2- = [P(Ph)(C6H3-3-Ph-2-S)2]2-), was obtained. Compound 3 cleaves the C-Cl bond in dichloromethane via an S-based nucleophilic attack to generate a chloromethyl thioether group. Two isomeric products, [Co(PS2*)(PSSCH2Cl*)] (4 and 4′) ([PSSCH2Cl*]- = [P(Ph)(C6H3-3-Ph-2-S)(C6H3-3-Ph-2-SCH2Cl)]-), were isolated and fully characterized. Both transformations, oxygenation of a CoII-bound phosphine donor in 1 and alkylation of a CoIII-bound thiolate in 3, were monitored by spectroscopic methods. These reaction products were isolated and fully characterized. Density functional theory (DFT, the B3LYP functional) calculations were performed to understand the electronic structure of 1 as well as the pathway of its transformation to 2.",

author = "Wu, {Yi Ying} and Hong, {Jia Cheng} and Tsai, {Ruei Fong} and Pan, {Hung Ruei} and Huang, {Bo Hua} and Chiang, {Yun Wei} and Lee, {Gene Hsiang} and Cheng, {Mu Jeng} and Hsu, {Hua Fen}",

note = "Funding Information: This work was supported by the Ministry of Science and Technology in Taiwan (MOST 107-2113-M-006-003, 107-2113-M-006-008-MY2, and 108-2113-M-007-029) and National Cheng Kung University in Taiwan. We thank Mr. Ming-Feng Chen and Mr. Tsung-Lun Kan in the Establishment of the Instrument Development Center at National Cheng Kung University for assisting with the measurements of ESI-MS data and NMR data. Publisher Copyright: {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = apr,

day = "6",

doi = "10.1021/acs.inorgchem.9b03740",

language = "English",

volume = "59",

pages = "4650--4660",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "7",

}

TY - JOUR

T1 - Ligand-Based Reactivity of Oxygenation and Alkylation in Cobalt Complexes Binding with (Thiolato)phosphine Derivatives

AU - Wu, Yi Ying

AU - Hong, Jia Cheng

AU - Tsai, Ruei Fong

AU - Pan, Hung Ruei

AU - Huang, Bo Hua

AU - Chiang, Yun Wei

AU - Lee, Gene Hsiang

AU - Cheng, Mu Jeng

AU - Hsu, Hua Fen

N1 - Funding Information: This work was supported by the Ministry of Science and Technology in Taiwan (MOST 107-2113-M-006-003, 107-2113-M-006-008-MY2, and 108-2113-M-007-029) and National Cheng Kung University in Taiwan. We thank Mr. Ming-Feng Chen and Mr. Tsung-Lun Kan in the Establishment of the Instrument Development Center at National Cheng Kung University for assisting with the measurements of ESI-MS data and NMR data. Publisher Copyright: © 2020 American Chemical Society.

PY - 2020/4/6

Y1 - 2020/4/6

N2 - In our efforts to understand the nature of metal thiolates, we have explored the chemistry of cobalt ion supported by (thiolato)phosphine ligand derivatives. Herein, we synthesized and characterized a square-planar CoII complex binding with a bidentate (thiolato)phosphine ligand, Co(PS1″)2 (1) ([PS1″]- = [P(Ph)2(C6H3-3-SiMe3-2-S)]-). The complex activates O2 to form a ligand-based oxygenation product, Co(OPS1″)2 (2) ([OPS1″]- = [PO(Ph)2(C6H3-3-SiMe3-2-S)]-). In addition, an octahedral CoIII complex with a tridentate bis(thiolato)phosphine ligand, [NEt4][Co(PS2*)2] (3) ([PS2*]2- = [P(Ph)(C6H3-3-Ph-2-S)2]2-), was obtained. Compound 3 cleaves the C-Cl bond in dichloromethane via an S-based nucleophilic attack to generate a chloromethyl thioether group. Two isomeric products, [Co(PS2*)(PSSCH2Cl*)] (4 and 4′) ([PSSCH2Cl*]- = [P(Ph)(C6H3-3-Ph-2-S)(C6H3-3-Ph-2-SCH2Cl)]-), were isolated and fully characterized. Both transformations, oxygenation of a CoII-bound phosphine donor in 1 and alkylation of a CoIII-bound thiolate in 3, were monitored by spectroscopic methods. These reaction products were isolated and fully characterized. Density functional theory (DFT, the B3LYP functional) calculations were performed to understand the electronic structure of 1 as well as the pathway of its transformation to 2.

AB - In our efforts to understand the nature of metal thiolates, we have explored the chemistry of cobalt ion supported by (thiolato)phosphine ligand derivatives. Herein, we synthesized and characterized a square-planar CoII complex binding with a bidentate (thiolato)phosphine ligand, Co(PS1″)2 (1) ([PS1″]- = [P(Ph)2(C6H3-3-SiMe3-2-S)]-). The complex activates O2 to form a ligand-based oxygenation product, Co(OPS1″)2 (2) ([OPS1″]- = [PO(Ph)2(C6H3-3-SiMe3-2-S)]-). In addition, an octahedral CoIII complex with a tridentate bis(thiolato)phosphine ligand, [NEt4][Co(PS2*)2] (3) ([PS2*]2- = [P(Ph)(C6H3-3-Ph-2-S)2]2-), was obtained. Compound 3 cleaves the C-Cl bond in dichloromethane via an S-based nucleophilic attack to generate a chloromethyl thioether group. Two isomeric products, [Co(PS2*)(PSSCH2Cl*)] (4 and 4′) ([PSSCH2Cl*]- = [P(Ph)(C6H3-3-Ph-2-S)(C6H3-3-Ph-2-SCH2Cl)]-), were isolated and fully characterized. Both transformations, oxygenation of a CoII-bound phosphine donor in 1 and alkylation of a CoIII-bound thiolate in 3, were monitored by spectroscopic methods. These reaction products were isolated and fully characterized. Density functional theory (DFT, the B3LYP functional) calculations were performed to understand the electronic structure of 1 as well as the pathway of its transformation to 2.

UR - http://www.scopus.com/inward/record.url?scp=85082078268&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85082078268&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.9b03740

DO - 10.1021/acs.inorgchem.9b03740

M3 - Article

C2 - 32186861

AN - SCOPUS:85082078268

SN - 0020-1669

VL - 59

SP - 4650

EP - 4660

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 7

ER -

Ligand-Based Reactivity of Oxygenation and Alkylation in Cobalt Complexes Binding with (Thiolato)phosphine Derivatives

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this