Sulfur difluoride and sulfur monofluoride as ligands in iron carbonyl chemistry

Xiaozhen Gao; Shida Gong; Nan Li; R. Bruce King

doi:10.1039/c5nj00460h

Sulfur difluoride and sulfur monofluoride as ligands in iron carbonyl chemistry

Xiaozhen Gao, Shida Gong, Nan Li^*, R. Bruce King

^*Corresponding author for this work

School of Mechatronical Engineering

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

4 Citations (Scopus)

Abstract

Density functional theory predicts a binuclear Fe₂(μ-SF₂)₂(CO)₈ octacarbonyl structure with two bridging SF₂ groups and a long Fe⋯Fe distance of ∼3.5 Å indicating a lack of a direct iron-iron bond. In addition, three Fe₂(μ-SF₂)(SF₂)(CO)₇ stereoisomers of similar energies are found with one bridging SF₂ group and one terminal SF₂ group and an even longer Fe⋯Fe distance of ∼3.9 Å likewise indicating a lack of a direct iron-iron bond. In contrast to the binuclear Fe₂(SF₂)₂(CO)_n (n = 8, 7) derivatives, the mononuclear Fe(SF₂)(CO)_n (n = 4, 3) are disfavored by ∼10 kcal mol^-1 for n = 4 to ∼30 kcal mol^-1 for n = 3, respectively, with respect to fluorine shift from sulfur to iron to give the corresponding Fe(SF)(F)(CO)_n derivatives. The SF ligands in the tetracarbonyls Fe(SF)(F)(CO)₄ are one-electron donor ligands with Fe-S distances of ∼2.3 Å. However, the SF ligands in the tricarbonyls Fe(SF)(F)(CO)₃ are three-electron donor ligands with significantly shorter FeS distances of ∼2.1

Original language	English
Pages (from-to)	4939-4947
Number of pages	9
Journal	New Journal of Chemistry
Volume	39
Issue number	6
DOIs	https://doi.org/10.1039/c5nj00460h
Publication status	Published - 1 Jun 2015

Access to Document

10.1039/c5nj00460h

Cite this

@article{63d2fcb46c6546f3b79cc5d886fbf796,

title = "Sulfur difluoride and sulfur monofluoride as ligands in iron carbonyl chemistry",

abstract = "Density functional theory predicts a binuclear Fe2(μ-SF2)2(CO)8 octacarbonyl structure with two bridging SF2 groups and a long Fe⋯Fe distance of ∼3.5 {\AA} indicating a lack of a direct iron-iron bond. In addition, three Fe2(μ-SF2)(SF2)(CO)7 stereoisomers of similar energies are found with one bridging SF2 group and one terminal SF2 group and an even longer Fe⋯Fe distance of ∼3.9 {\AA} likewise indicating a lack of a direct iron-iron bond. In contrast to the binuclear Fe2(SF2)2(CO)n (n = 8, 7) derivatives, the mononuclear Fe(SF2)(CO)n (n = 4, 3) are disfavored by ∼10 kcal mol-1 for n = 4 to ∼30 kcal mol-1 for n = 3, respectively, with respect to fluorine shift from sulfur to iron to give the corresponding Fe(SF)(F)(CO)n derivatives. The SF ligands in the tetracarbonyls Fe(SF)(F)(CO)4 are one-electron donor ligands with Fe-S distances of ∼2.3 {\AA}. However, the SF ligands in the tricarbonyls Fe(SF)(F)(CO)3 are three-electron donor ligands with significantly shorter FeS distances of ∼2.1",

author = "Xiaozhen Gao and Shida Gong and Nan Li and {Bruce King}, R.",

note = "Publisher Copyright: {\textcopyright} The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.",

year = "2015",

month = jun,

day = "1",

doi = "10.1039/c5nj00460h",

language = "English",

volume = "39",

pages = "4939--4947",

journal = "New Journal of Chemistry",

issn = "1144-0546",

publisher = "Royal Society of Chemistry",

number = "6",

}

TY - JOUR

T1 - Sulfur difluoride and sulfur monofluoride as ligands in iron carbonyl chemistry

AU - Gao, Xiaozhen

AU - Gong, Shida

AU - Li, Nan

AU - Bruce King, R.

PY - 2015/6/1

Y1 - 2015/6/1

N2 - Density functional theory predicts a binuclear Fe2(μ-SF2)2(CO)8 octacarbonyl structure with two bridging SF2 groups and a long Fe⋯Fe distance of ∼3.5 Å indicating a lack of a direct iron-iron bond. In addition, three Fe2(μ-SF2)(SF2)(CO)7 stereoisomers of similar energies are found with one bridging SF2 group and one terminal SF2 group and an even longer Fe⋯Fe distance of ∼3.9 Å likewise indicating a lack of a direct iron-iron bond. In contrast to the binuclear Fe2(SF2)2(CO)n (n = 8, 7) derivatives, the mononuclear Fe(SF2)(CO)n (n = 4, 3) are disfavored by ∼10 kcal mol-1 for n = 4 to ∼30 kcal mol-1 for n = 3, respectively, with respect to fluorine shift from sulfur to iron to give the corresponding Fe(SF)(F)(CO)n derivatives. The SF ligands in the tetracarbonyls Fe(SF)(F)(CO)4 are one-electron donor ligands with Fe-S distances of ∼2.3 Å. However, the SF ligands in the tricarbonyls Fe(SF)(F)(CO)3 are three-electron donor ligands with significantly shorter FeS distances of ∼2.1

AB - Density functional theory predicts a binuclear Fe2(μ-SF2)2(CO)8 octacarbonyl structure with two bridging SF2 groups and a long Fe⋯Fe distance of ∼3.5 Å indicating a lack of a direct iron-iron bond. In addition, three Fe2(μ-SF2)(SF2)(CO)7 stereoisomers of similar energies are found with one bridging SF2 group and one terminal SF2 group and an even longer Fe⋯Fe distance of ∼3.9 Å likewise indicating a lack of a direct iron-iron bond. In contrast to the binuclear Fe2(SF2)2(CO)n (n = 8, 7) derivatives, the mononuclear Fe(SF2)(CO)n (n = 4, 3) are disfavored by ∼10 kcal mol-1 for n = 4 to ∼30 kcal mol-1 for n = 3, respectively, with respect to fluorine shift from sulfur to iron to give the corresponding Fe(SF)(F)(CO)n derivatives. The SF ligands in the tetracarbonyls Fe(SF)(F)(CO)4 are one-electron donor ligands with Fe-S distances of ∼2.3 Å. However, the SF ligands in the tricarbonyls Fe(SF)(F)(CO)3 are three-electron donor ligands with significantly shorter FeS distances of ∼2.1

UR - http://www.scopus.com/inward/record.url?scp=84930627209&partnerID=8YFLogxK

U2 - 10.1039/c5nj00460h

DO - 10.1039/c5nj00460h

M3 - Article

AN - SCOPUS:84930627209

SN - 1144-0546

VL - 39

SP - 4939

EP - 4947

JO - New Journal of Chemistry

JF - New Journal of Chemistry

IS - 6

ER -

Sulfur difluoride and sulfur monofluoride as ligands in iron carbonyl chemistry

Abstract

Access to Document

Other files and links

Fingerprint

Cite this