Pnictogen ligand coordination to an iron-sulfur compound

Elizabeth S. Donovan; Hannah M. Plummer; Alberto Sosa Parada; Gary S. Nichol; Greg A.N. Felton

doi:10.1016/j.ica.2018.12.035

Pnictogen ligand coordination to an iron-sulfur compound

Elizabeth S. Donovan, Hannah M. Plummer, Alberto Sosa Parada, Gary S. Nichol, Greg A.N. Felton^*

^*Corresponding author for this work

School of Chemistry

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

Abstract

The effect of replacing one CO ligand of the competent proton reduction electrocatalyst [(μ-Cl₂-bdt)Fe₂(CO)₆] (“Cl₂-bdt” = 3,6-dichloro-1,2-benzenedithiolato), A, with a pnictogen-based ligand has been explored. Four novel compounds have been synthesized and characterized, including X-ray crystallographic structures: [Fe₂(µ-Cl₂-bdt)(CO)₅PPh₃] (1), [Fe₂(µ-Cl₂-bdt)(CO)₅AsPh₃] (2), [Fe₂(µ-Cl₂-bdt)(CO)₅Sb(O)PPh₃] (3), and [Fe₂(µ-Cl₂-bdt)(CO)₄(SbPPh₃)₂] (4). Notably, 3 represents an uncommon hypervalent antimony 12-Sb-5 compound. The three mono-pnictogen compounds (1–3) were produced in yields of 44–58% and have been investigated electrochemically. Evaluation for electrocatalytic formation of dihydrogen in the presence of acetic acid for compounds 1–3 shows negligible advantage over compound A.

Original language	English
Pages (from-to)	387-394
Number of pages	8
Journal	Inorganica Chimica Acta
Volume	487
Early online date	24 Dec 2018
DOIs	https://doi.org/10.1016/j.ica.2018.12.035
Publication status	E-pub ahead of print - 24 Dec 2018

Keywords / Materials (for Non-textual outputs)

Electrocatalysis
Hydrogenase model
Hypervalent antimony
Iron-sulfur
Pnictogen

Access to Document

10.1016/j.ica.2018.12.035

Cite this

@article{7097aacf09a04487b69caf02d8137b74,

title = "Pnictogen ligand coordination to an iron-sulfur compound",

abstract = "The effect of replacing one CO ligand of the competent proton reduction electrocatalyst [(μ-Cl2-bdt)Fe2(CO)6] (“Cl2-bdt” = 3,6-dichloro-1,2-benzenedithiolato), A, with a pnictogen-based ligand has been explored. Four novel compounds have been synthesized and characterized, including X-ray crystallographic structures: [Fe2(µ-Cl2-bdt)(CO)5PPh3] (1), [Fe2(µ-Cl2-bdt)(CO)5AsPh3] (2), [Fe2(µ-Cl2-bdt)(CO)5Sb(O)PPh3] (3), and [Fe2(µ-Cl2-bdt)(CO)4(SbPPh3)2] (4). Notably, 3 represents an uncommon hypervalent antimony 12-Sb-5 compound. The three mono-pnictogen compounds (1–3) were produced in yields of 44–58\% and have been investigated electrochemically. Evaluation for electrocatalytic formation of dihydrogen in the presence of acetic acid for compounds 1–3 shows negligible advantage over compound A.",

keywords = "Electrocatalysis, Hydrogenase model, Hypervalent antimony, Iron-sulfur, Pnictogen",

author = "Donovan, \{Elizabeth S.\} and Plummer, \{Hannah M.\} and Parada, \{Alberto Sosa\} and Nichol, \{Gary S.\} and Felton, \{Greg A.N.\}",

note = "Publisher Copyright: {\textcopyright} 2018 Elsevier B.V.",

year = "2018",

month = dec,

day = "24",

doi = "10.1016/j.ica.2018.12.035",

language = "English",

volume = "487",

pages = "387--394",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

publisher = "Elsevier",

}

TY - JOUR

T1 - Pnictogen ligand coordination to an iron-sulfur compound

AU - Donovan, Elizabeth S.

AU - Plummer, Hannah M.

AU - Parada, Alberto Sosa

AU - Nichol, Gary S.

AU - Felton, Greg A.N.

PY - 2018/12/24

Y1 - 2018/12/24

N2 - The effect of replacing one CO ligand of the competent proton reduction electrocatalyst [(μ-Cl2-bdt)Fe2(CO)6] (“Cl2-bdt” = 3,6-dichloro-1,2-benzenedithiolato), A, with a pnictogen-based ligand has been explored. Four novel compounds have been synthesized and characterized, including X-ray crystallographic structures: [Fe2(µ-Cl2-bdt)(CO)5PPh3] (1), [Fe2(µ-Cl2-bdt)(CO)5AsPh3] (2), [Fe2(µ-Cl2-bdt)(CO)5Sb(O)PPh3] (3), and [Fe2(µ-Cl2-bdt)(CO)4(SbPPh3)2] (4). Notably, 3 represents an uncommon hypervalent antimony 12-Sb-5 compound. The three mono-pnictogen compounds (1–3) were produced in yields of 44–58% and have been investigated electrochemically. Evaluation for electrocatalytic formation of dihydrogen in the presence of acetic acid for compounds 1–3 shows negligible advantage over compound A.

AB - The effect of replacing one CO ligand of the competent proton reduction electrocatalyst [(μ-Cl2-bdt)Fe2(CO)6] (“Cl2-bdt” = 3,6-dichloro-1,2-benzenedithiolato), A, with a pnictogen-based ligand has been explored. Four novel compounds have been synthesized and characterized, including X-ray crystallographic structures: [Fe2(µ-Cl2-bdt)(CO)5PPh3] (1), [Fe2(µ-Cl2-bdt)(CO)5AsPh3] (2), [Fe2(µ-Cl2-bdt)(CO)5Sb(O)PPh3] (3), and [Fe2(µ-Cl2-bdt)(CO)4(SbPPh3)2] (4). Notably, 3 represents an uncommon hypervalent antimony 12-Sb-5 compound. The three mono-pnictogen compounds (1–3) were produced in yields of 44–58% and have been investigated electrochemically. Evaluation for electrocatalytic formation of dihydrogen in the presence of acetic acid for compounds 1–3 shows negligible advantage over compound A.

KW - Electrocatalysis

KW - Hydrogenase model

KW - Hypervalent antimony

KW - Iron-sulfur

KW - Pnictogen

U2 - 10.1016/j.ica.2018.12.035

DO - 10.1016/j.ica.2018.12.035

M3 - Article

AN - SCOPUS:85059348463

SN - 0020-1693

VL - 487

SP - 387

EP - 394

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

ER -

Pnictogen ligand coordination to an iron-sulfur compound

Abstract

Keywords / Materials (for Non-textual outputs)

Access to Document

Fingerprint

Cite this