Cyanate groups in higher oxidation state metal cluster chemistry: Mixed-valence (II/III) Mn16 and Mn18 clusters

Dimitris I. Alexandropoulos; Eleni E. Moushi; Constantina Papatriantafyllopoulou; Christine M. Beavers; Simon J. Teat; Anastasios J. Tasiopoulos; George Christou; Theocharis C. Stamatatos

doi:10.1016/j.poly.2015.11.031

Cyanate groups in higher oxidation state metal cluster chemistry: Mixed-valence (II/III) Mn₁₆ and Mn₁₈ clusters

Dimitris I. Alexandropoulos
, Eleni E. Moushi
, Constantina Papatriantafyllopoulou
, Christine M. Beavers
, Simon J. Teat
, Anastasios J. Tasiopoulos
, George Christou
, Theocharis C. Stamatatos

Brock University
University of Cyprus
University of Florida
Advanced Light Source, Berkeley

Research output: Contribution to a Journal (Peer & Non Peer) › Article › peer-review

6 Citations (Scopus)

Abstract

The employment of cyanato (OCN^-) group in high oxidation state manganese cluster chemistry, in conjunction with carboxylate ions and the organic chelating/bridging ligand 2-(hydroxymethyl)pyridine (hmpH), is reported. The syntheses, crystal structures, and magnetochemical characterization are described for [Mn₁₆O₈(OR)₄(OCN)₄(O₂CMe)₁₂(hmp)₆(ROH)₂] (R = Me (1), Et (2)) and [Mn₁₈O₁₄(O₂CR)₁₈(hmp)₄(hmpH)₂(H₂O)₂] (R = Me (3), Et (4)). The 2:1:1:1 reactions of Mn(O₂CMe)₂·4H₂O, hmpH, NaOCN and NEt₃ in solvent MeOH or EtOH afford the isostructural complexes [Mn₁₆O₈(OR)₄(OCN)₄(O₂CMe)₁₂(hmp)₆(ROH)₂] (R = Me (1), Et (2)). The [Mn₁₆(μ₄-O)₄(μ₃-O)₄(μ-OMe)₄(μ₃-OR)₆(μ-OR)₆]¹⁰⁺ core of representative complex 1 comprises a Mn^II₄Mn^III₄ double-cubane subunit attached on either side to two symmetry-related Mn^IIMn^III₃ defective dicubanes. A similar reaction of Mn(O₂CR)₂·4H₂O, hmpH, NaOCN and NEt₃, but in solvent MeCN, led instead to the formation of [Mn₁₈O₁₄(O₂CR)₁₈(hmp)₄(hmpH)₂(H₂O)₂] (R = Me (3), Et (4)). Compounds 3 and 4 are very similar to each other and can be described as a central [Mn^III₄(μ-O)₆] rodlike subunit attached on either side to two symmetry-related [Mn₇O₉] subunits. Variable-temperature, solid-state dc and ac magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions in all compounds, and possible S = 2 or 1 (for 1 and 2) and S = 0 (for 3 and 4) ground state spin values. The combined results demonstrate the ability of cyanato groups to facilitate the formation of new polynuclear Mn^II/III complexes with structures different than these obtained from the use of the related azides.

Original language	English
Pages (from-to)	131-142
Number of pages	12
Journal	Polyhedron
Volume	108
DOIs	https://doi.org/10.1016/j.poly.2015.11.031
Publication status	Published - 29 Mar 2016
Externally published	Yes

Keywords

2-(Hydroxymethyl)pyridine
Crystal structures
Cyanates
Magnetism
Manganese

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10.1016/j.poly.2015.11.031

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@article{77075227b26c40beb5f023c5d655056f,

title = "Cyanate groups in higher oxidation state metal cluster chemistry: Mixed-valence (II/III) Mn16 and Mn18 clusters",

abstract = "The employment of cyanato (OCN-) group in high oxidation state manganese cluster chemistry, in conjunction with carboxylate ions and the organic chelating/bridging ligand 2-(hydroxymethyl)pyridine (hmpH), is reported. The syntheses, crystal structures, and magnetochemical characterization are described for [Mn16O8(OR)4(OCN)4(O2CMe)12(hmp)6(ROH)2] (R = Me (1), Et (2)) and [Mn18O14(O2CR)18(hmp)4(hmpH)2(H2O)2] (R = Me (3), Et (4)). The 2:1:1:1 reactions of Mn(O2CMe)2·4H2O, hmpH, NaOCN and NEt3 in solvent MeOH or EtOH afford the isostructural complexes [Mn16O8(OR)4(OCN)4(O2CMe)12(hmp)6(ROH)2] (R = Me (1), Et (2)). The [Mn16(μ4-O)4(μ3-O)4(μ-OMe)4(μ3-OR)6(μ-OR)6]10+ core of representative complex 1 comprises a MnII4MnIII4 double-cubane subunit attached on either side to two symmetry-related MnIIMnIII3 defective dicubanes. A similar reaction of Mn(O2CR)2·4H2O, hmpH, NaOCN and NEt3, but in solvent MeCN, led instead to the formation of [Mn18O14(O2CR)18(hmp)4(hmpH)2(H2O)2] (R = Me (3), Et (4)). Compounds 3 and 4 are very similar to each other and can be described as a central [MnIII4(μ-O)6] rodlike subunit attached on either side to two symmetry-related [Mn7O9] subunits. Variable-temperature, solid-state dc and ac magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions in all compounds, and possible S = 2 or 1 (for 1 and 2) and S = 0 (for 3 and 4) ground state spin values. The combined results demonstrate the ability of cyanato groups to facilitate the formation of new polynuclear MnII/III complexes with structures different than these obtained from the use of the related azides.",

keywords = "2-(Hydroxymethyl)pyridine, Crystal structures, Cyanates, Magnetism, Manganese",

author = "Alexandropoulos, \{Dimitris I.\} and Moushi, \{Eleni E.\} and Constantina Papatriantafyllopoulou and Beavers, \{Christine M.\} and Teat, \{Simon J.\} and Tasiopoulos, \{Anastasios J.\} and George Christou and Stamatatos, \{Theocharis C.\}",

year = "2016",

month = mar,

day = "29",

doi = "10.1016/j.poly.2015.11.031",

language = "English",

volume = "108",

pages = "131--142",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Ltd",

}

TY - JOUR

T1 - Cyanate groups in higher oxidation state metal cluster chemistry

T2 - Mixed-valence (II/III) Mn16 and Mn18 clusters

AU - Alexandropoulos, Dimitris I.

AU - Moushi, Eleni E.

AU - Papatriantafyllopoulou, Constantina

AU - Beavers, Christine M.

AU - Teat, Simon J.

AU - Tasiopoulos, Anastasios J.

AU - Christou, George

AU - Stamatatos, Theocharis C.

PY - 2016/3/29

Y1 - 2016/3/29

N2 - The employment of cyanato (OCN-) group in high oxidation state manganese cluster chemistry, in conjunction with carboxylate ions and the organic chelating/bridging ligand 2-(hydroxymethyl)pyridine (hmpH), is reported. The syntheses, crystal structures, and magnetochemical characterization are described for [Mn16O8(OR)4(OCN)4(O2CMe)12(hmp)6(ROH)2] (R = Me (1), Et (2)) and [Mn18O14(O2CR)18(hmp)4(hmpH)2(H2O)2] (R = Me (3), Et (4)). The 2:1:1:1 reactions of Mn(O2CMe)2·4H2O, hmpH, NaOCN and NEt3 in solvent MeOH or EtOH afford the isostructural complexes [Mn16O8(OR)4(OCN)4(O2CMe)12(hmp)6(ROH)2] (R = Me (1), Et (2)). The [Mn16(μ4-O)4(μ3-O)4(μ-OMe)4(μ3-OR)6(μ-OR)6]10+ core of representative complex 1 comprises a MnII4MnIII4 double-cubane subunit attached on either side to two symmetry-related MnIIMnIII3 defective dicubanes. A similar reaction of Mn(O2CR)2·4H2O, hmpH, NaOCN and NEt3, but in solvent MeCN, led instead to the formation of [Mn18O14(O2CR)18(hmp)4(hmpH)2(H2O)2] (R = Me (3), Et (4)). Compounds 3 and 4 are very similar to each other and can be described as a central [MnIII4(μ-O)6] rodlike subunit attached on either side to two symmetry-related [Mn7O9] subunits. Variable-temperature, solid-state dc and ac magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions in all compounds, and possible S = 2 or 1 (for 1 and 2) and S = 0 (for 3 and 4) ground state spin values. The combined results demonstrate the ability of cyanato groups to facilitate the formation of new polynuclear MnII/III complexes with structures different than these obtained from the use of the related azides.

AB - The employment of cyanato (OCN-) group in high oxidation state manganese cluster chemistry, in conjunction with carboxylate ions and the organic chelating/bridging ligand 2-(hydroxymethyl)pyridine (hmpH), is reported. The syntheses, crystal structures, and magnetochemical characterization are described for [Mn16O8(OR)4(OCN)4(O2CMe)12(hmp)6(ROH)2] (R = Me (1), Et (2)) and [Mn18O14(O2CR)18(hmp)4(hmpH)2(H2O)2] (R = Me (3), Et (4)). The 2:1:1:1 reactions of Mn(O2CMe)2·4H2O, hmpH, NaOCN and NEt3 in solvent MeOH or EtOH afford the isostructural complexes [Mn16O8(OR)4(OCN)4(O2CMe)12(hmp)6(ROH)2] (R = Me (1), Et (2)). The [Mn16(μ4-O)4(μ3-O)4(μ-OMe)4(μ3-OR)6(μ-OR)6]10+ core of representative complex 1 comprises a MnII4MnIII4 double-cubane subunit attached on either side to two symmetry-related MnIIMnIII3 defective dicubanes. A similar reaction of Mn(O2CR)2·4H2O, hmpH, NaOCN and NEt3, but in solvent MeCN, led instead to the formation of [Mn18O14(O2CR)18(hmp)4(hmpH)2(H2O)2] (R = Me (3), Et (4)). Compounds 3 and 4 are very similar to each other and can be described as a central [MnIII4(μ-O)6] rodlike subunit attached on either side to two symmetry-related [Mn7O9] subunits. Variable-temperature, solid-state dc and ac magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions in all compounds, and possible S = 2 or 1 (for 1 and 2) and S = 0 (for 3 and 4) ground state spin values. The combined results demonstrate the ability of cyanato groups to facilitate the formation of new polynuclear MnII/III complexes with structures different than these obtained from the use of the related azides.

KW - 2-(Hydroxymethyl)pyridine

KW - Crystal structures

KW - Cyanates

KW - Magnetism

KW - Manganese

UR - https://www.scopus.com/pages/publications/84950124634

U2 - 10.1016/j.poly.2015.11.031

DO - 10.1016/j.poly.2015.11.031

M3 - Article

SN - 0277-5387

VL - 108

SP - 131

EP - 142

JO - Polyhedron

JF - Polyhedron

ER -

Cyanate groups in higher oxidation state metal cluster chemistry: Mixed-valence (II/III) Mn₁₆ and Mn₁₈ clusters

Abstract

Keywords

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