Coordination properties of non-rigid phosphinoyldithioformate complexes of the [mo2 o2 (µ-s)2 ]2+ cation in catalytic sulfur transfer reactions with thiiranes

Dmitrii Razinkov; Hafdís I. Ingvarsdottir; Ágúst Kvaran; Sigridur Jonsdottir; Sigridur G. Suman

doi:10.3390/catal11050593

Coordination properties of non-rigid phosphinoyldithioformate complexes of the [mo₂ o₂ (µ-s)₂ ]²⁺ cation in catalytic sulfur transfer reactions with thiiranes

Dmitrii Razinkov, Hafdís I. Ingvarsdottir, Ágúst Kvaran, Sigridur Jonsdottir, Sigridur G. Suman

University of Iceland

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

Abstract

Two “Mo₂ O₂ S₂ ”-based complexes with phosphinoyldithioformate ligands were synthesized from the metathesis reaction of [R₂ P(O)CS₂ ]⁻ with (Me₄ N)₂ [Mo₂ O₂ (µ-S)₂ (Cl)₄ ] to give [Mo₂ O₂ (µ-S)₂ {R₂ P(O)CS₂ }₂ ] (1; R = Ph, 2; R = Bn). The complexes were fully characterized, including the X-ray crystal structure for 1. Variable temperatures³¹ P NMR of 1 and 2 exhibit non-rigid behavior in solution where three and two coordination isomers were present, respectively. The organic sub-stituent on the P atom greatly impacts the complex non-rigid properties and behavior. The catalytic activity of 1 and 2 towards sulfur atom transfer (SAT) using propylene sulfide and cyclohexene sulfide was explored, employing homogeneous reaction conditions at an ambient temperature on the NMR scale. The complexes showed distinctly different properties along with high conversions in short reaction times. A catalytic cycle consistent with the results is proposed.

Original language	English
Article number	593
Journal	Catalysts
Volume	11
Issue number	5
DOIs	https://doi.org/10.3390/catal11050593
Publication status	Published - 4 May 2021

Bibliographical note

Funding Information: Funding: This research was funded by Icelandic Centre of Research, grant number 173667 and by University of Iceland Research Fund. The Icelandic Centre of Research infrastructure grant number (X-ray diffractometer; 150998-0031). Publisher Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland.

Other keywords

Catalysis
Cyclohexene sulfide
Molybdenum
Propylene sulfide
Sulfur
Thiiranes

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.3390/catal11050593

Cite this

@article{889fb01f7bc04a128ba10b1cd7e8ef86,

title = "Coordination properties of non-rigid phosphinoyldithioformate complexes of the [mo2 o2 (µ-s)2 ]2+ cation in catalytic sulfur transfer reactions with thiiranes",

abstract = "Two “Mo2 O2 S2 ”-based complexes with phosphinoyldithioformate ligands were synthesized from the metathesis reaction of [R2 P(O)CS2 ]− with (Me4 N)2 [Mo2 O2 (µ-S)2 (Cl)4 ] to give [Mo2 O2 (µ-S)2 \{R2 P(O)CS2 \}2 ] (1; R = Ph, 2; R = Bn). The complexes were fully characterized, including the X-ray crystal structure for 1. Variable temperatures31 P NMR of 1 and 2 exhibit non-rigid behavior in solution where three and two coordination isomers were present, respectively. The organic sub-stituent on the P atom greatly impacts the complex non-rigid properties and behavior. The catalytic activity of 1 and 2 towards sulfur atom transfer (SAT) using propylene sulfide and cyclohexene sulfide was explored, employing homogeneous reaction conditions at an ambient temperature on the NMR scale. The complexes showed distinctly different properties along with high conversions in short reaction times. A catalytic cycle consistent with the results is proposed.",

keywords = "Catalysis, Cyclohexene sulfide, Molybdenum, Propylene sulfide, Sulfur, Thiiranes",

author = "Dmitrii Razinkov and Ingvarsdottir, \{Hafd{\'i}s I.\} and {\'A}g{\'u}st Kvaran and Sigridur Jonsdottir and Suman, \{Sigridur G.\}",

note = "Funding Information: Funding: This research was funded by Icelandic Centre of Research, grant number 173667 and by University of Iceland Research Fund. The Icelandic Centre of Research infrastructure grant number (X-ray diffractometer; 150998-0031). Publisher Copyright: {\textcopyright} 2021 by the authors. Licensee MDPI, Basel, Switzerland.",

year = "2021",

month = may,

day = "4",

doi = "10.3390/catal11050593",

language = "English",

volume = "11",

journal = "Catalysts",

issn = "2073-4344",

publisher = "Multidisciplinary Digital Publishing Institute (MDPI)",

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TY - JOUR

T1 - Coordination properties of non-rigid phosphinoyldithioformate complexes of the [mo2 o2 (µ-s)2 ]2+ cation in catalytic sulfur transfer reactions with thiiranes

AU - Razinkov, Dmitrii

AU - Ingvarsdottir, Hafdís I.

AU - Kvaran, Ágúst

AU - Jonsdottir, Sigridur

AU - Suman, Sigridur G.

N1 - Funding Information: Funding: This research was funded by Icelandic Centre of Research, grant number 173667 and by University of Iceland Research Fund. The Icelandic Centre of Research infrastructure grant number (X-ray diffractometer; 150998-0031). Publisher Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland.

PY - 2021/5/4

Y1 - 2021/5/4

N2 - Two “Mo2 O2 S2 ”-based complexes with phosphinoyldithioformate ligands were synthesized from the metathesis reaction of [R2 P(O)CS2 ]− with (Me4 N)2 [Mo2 O2 (µ-S)2 (Cl)4 ] to give [Mo2 O2 (µ-S)2 {R2 P(O)CS2 }2 ] (1; R = Ph, 2; R = Bn). The complexes were fully characterized, including the X-ray crystal structure for 1. Variable temperatures31 P NMR of 1 and 2 exhibit non-rigid behavior in solution where three and two coordination isomers were present, respectively. The organic sub-stituent on the P atom greatly impacts the complex non-rigid properties and behavior. The catalytic activity of 1 and 2 towards sulfur atom transfer (SAT) using propylene sulfide and cyclohexene sulfide was explored, employing homogeneous reaction conditions at an ambient temperature on the NMR scale. The complexes showed distinctly different properties along with high conversions in short reaction times. A catalytic cycle consistent with the results is proposed.

AB - Two “Mo2 O2 S2 ”-based complexes with phosphinoyldithioformate ligands were synthesized from the metathesis reaction of [R2 P(O)CS2 ]− with (Me4 N)2 [Mo2 O2 (µ-S)2 (Cl)4 ] to give [Mo2 O2 (µ-S)2 {R2 P(O)CS2 }2 ] (1; R = Ph, 2; R = Bn). The complexes were fully characterized, including the X-ray crystal structure for 1. Variable temperatures31 P NMR of 1 and 2 exhibit non-rigid behavior in solution where three and two coordination isomers were present, respectively. The organic sub-stituent on the P atom greatly impacts the complex non-rigid properties and behavior. The catalytic activity of 1 and 2 towards sulfur atom transfer (SAT) using propylene sulfide and cyclohexene sulfide was explored, employing homogeneous reaction conditions at an ambient temperature on the NMR scale. The complexes showed distinctly different properties along with high conversions in short reaction times. A catalytic cycle consistent with the results is proposed.

KW - Catalysis

KW - Cyclohexene sulfide

KW - Molybdenum

KW - Propylene sulfide

KW - Sulfur

KW - Thiiranes

UR - https://www.scopus.com/pages/publications/85105193131

U2 - 10.3390/catal11050593

DO - 10.3390/catal11050593

M3 - Article

SN - 2073-4344

VL - 11

JO - Catalysts

JF - Catalysts

IS - 5

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ER -