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Synthesis of mixed salts of the [Mo2O2(μ-S)2(SCN)6-n(L)n](4+n)− anion (n = 0–2); structures of [Mo2O2(μ-S)2(SCN)5(CH3CN)]3−, [Mo2O2(μ-S)2(CN)5]3−, and [Mo2O2(μ-S)2(CN)2(O)]2−, and probing the ligand exchange of thiocyanate and cyanide

Suman, Sigridur G. ; Snæbjörnsson, Thorvaldur ; Ragnarsdóttir, Oddný ; Polukeev, Alexey V. LU and Wendt, Ola F. LU (2021) In Polyhedron 209.
Abstract

Aqueous coordination of cyanide and verification of the composition of the resulting coordination compound is important to ensure confidence in its coordination. Isothiocyanato compounds 1–7 were synthesized employing different synthetic routes and the complex, [Mo2O2(μ-S)2(SCN)5(CH3CN)]3−, 4, was structurally characterized. Ligand exchange reaction of 4 with cyanide forms 8, a cyano complex. Complex 8 was isolated as an organosoluble salt and fully characterized and confirmed as the major product formed in the aqueous ligand exchange reaction of 4–7 with cyanide. The crystal structure of 8 revealed the unusual... (More)

Aqueous coordination of cyanide and verification of the composition of the resulting coordination compound is important to ensure confidence in its coordination. Isothiocyanato compounds 1–7 were synthesized employing different synthetic routes and the complex, [Mo2O2(μ-S)2(SCN)5(CH3CN)]3−, 4, was structurally characterized. Ligand exchange reaction of 4 with cyanide forms 8, a cyano complex. Complex 8 was isolated as an organosoluble salt and fully characterized and confirmed as the major product formed in the aqueous ligand exchange reaction of 4–7 with cyanide. The crystal structure of 8 revealed the unusual [Mo2O2(μ-S)2(CN)5]3− anion where the two molybdenum(V) centers are unsymmetrically coordinated. A second unsymmetric cyano complex [Mo2O3(μ-S)2(CN)2]2− 9, presumed hydrolysis product from an aqueous reaction, was isolated and structurally characterized revealing one square pyramidal Mo center and one tetrahedral Mo center in the binuclear core. Attempts to quantify the first order dissociative ligand substitution rate of thiocyanate in 4 to form 8 using the stopped-flow method gave an estimated minimum rate constant of 70 s−1. This confirms that the exchange reaction is sufficiently fast to be useful in aqueous coordination of cyanide.

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author
; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Cyano, Molybdenum, Thiocyanato
in
Polyhedron
volume
209
article number
115447
publisher
Elsevier
external identifiers
  • scopus:85114178592
ISSN
0277-5387
DOI
10.1016/j.poly.2021.115447
language
English
LU publication?
yes
id
113b6877-1715-476a-8fb4-706d46f1a406
date added to LUP
2021-10-08 13:47:41
date last changed
2025-04-04 14:02:34
@article{113b6877-1715-476a-8fb4-706d46f1a406,
  abstract     = {{<p>Aqueous coordination of cyanide and verification of the composition of the resulting coordination compound is important to ensure confidence in its coordination. Isothiocyanato compounds 1–7 were synthesized employing different synthetic routes and the complex, [Mo<sub>2</sub>O<sub>2</sub>(μ-S)<sub>2</sub>(SCN)<sub>5</sub>(CH<sub>3</sub>CN)]<sup>3−</sup>, 4, was structurally characterized. Ligand exchange reaction of 4 with cyanide forms 8, a cyano complex. Complex 8 was isolated as an organosoluble salt and fully characterized and confirmed as the major product formed in the aqueous ligand exchange reaction of 4–7 with cyanide. The crystal structure of 8 revealed the unusual [Mo<sub>2</sub>O<sub>2</sub>(μ-S)<sub>2</sub>(CN)<sub>5</sub>]<sup>3−</sup> anion where the two molybdenum(V) centers are unsymmetrically coordinated. A second unsymmetric cyano complex [Mo<sub>2</sub>O<sub>3</sub>(μ-S)<sub>2</sub>(CN)<sub>2</sub>]<sup>2−</sup> 9, presumed hydrolysis product from an aqueous reaction, was isolated and structurally characterized revealing one square pyramidal Mo center and one tetrahedral Mo center in the binuclear core. Attempts to quantify the first order dissociative ligand substitution rate of thiocyanate in 4 to form 8 using the stopped-flow method gave an estimated minimum rate constant of 70 s<sup>−1</sup>. This confirms that the exchange reaction is sufficiently fast to be useful in aqueous coordination of cyanide.</p>}},
  author       = {{Suman, Sigridur G. and Snæbjörnsson, Thorvaldur and Ragnarsdóttir, Oddný and Polukeev, Alexey V. and Wendt, Ola F.}},
  issn         = {{0277-5387}},
  keywords     = {{Cyano; Molybdenum; Thiocyanato}},
  language     = {{eng}},
  publisher    = {{Elsevier}},
  series       = {{Polyhedron}},
  title        = {{Synthesis of mixed salts of the [Mo<sub>2</sub>O<sub>2</sub>(μ-S)<sub>2</sub>(SCN)<sub>6-n</sub>(L)<sub>n</sub>]<sup>(4+n)</sup><sup>−</sup> anion (n = 0–2); structures of [Mo<sub>2</sub>O<sub>2</sub>(μ-S)<sub>2</sub>(SCN)<sub>5</sub>(CH<sub>3</sub>CN)]<sup>3−</sup>, [Mo<sub>2</sub>O<sub>2</sub>(μ-S)<sub>2</sub>(CN)<sub>5</sub>]<sup>3−</sup>, and [Mo<sub>2</sub>O<sub>2</sub>(μ-S)<sub>2</sub>(CN)<sub>2</sub>(O)]<sup>2−</sup>, and probing the ligand exchange of thiocyanate and cyanide}},
  url          = {{http://dx.doi.org/10.1016/j.poly.2021.115447}},
  doi          = {{10.1016/j.poly.2021.115447}},
  volume       = {{209}},
  year         = {{2021}},
}