Aqueous reduction of [Cp*2W2O5]: Characterization of the triangular clusters [Cp*3W 3O4(OH)2]2+ and [Cp* 3W3O6]+ - Comparison with molybdenum

Chiara Dinoi; Pelin Sözen; Gülnur Taban; Deniz Demir; Funda Demirhan; Petr Prikhodchenko; Jenny Gun; Ovadia Lev; Jean Claude Daran; Rinaldo Poli

doi:10.1002/ejic.200700419

Aqueous reduction of [Cp₂W₂O₅]: Characterization of the triangular clusters [Cp₃W ₃O₄(OH)₂]²⁺ and [Cp* ₃W₃O₆]⁺ - Comparison with molybdenum

Chiara Dinoi, Pelin Sözen, Gülnur Taban, Deniz Demir, Funda Demirhan^*, Petr Prikhodchenko, Jenny Gun, Ovadia Lev, Jean Claude Daran, Rinaldo Poli

^*Corresponding author for this work

Institute of Chemistry

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

11 Scopus citations

Abstract

Zinc reduction of Cp*₂W₂O₅ in an acidified water-methanol medium affords the green 3-electron trinuclear cluster [Cp*₃W₃O₄(OH)₂]²⁺, isolated and crystallographically characterized as the triflate salt, 1. Upon exposure to air, this complex is oxidized to a related 2-electron cluster, [Cp*₃W₃O₆]⁺, which was crystallized and characterized in three different salts, 2-4. The 3-electron cluster exhibits a near-tetragonal frozen-glass EPR spectrum, and it shows evidence of coupling of the unpaired electron to only one of the three W atoms. The two-electron cluster is diamagnetic. An electrospray ionization MS ⁿ study revealed a stepwise expulsion of neutral [Cp*WO ₂] units as the main fragmentation process. DFT calculations unveiled the intimate details of the electronic structures of these complexes and fully rationalized the structural and spectroscopic properties.

Original language	American English
Pages (from-to)	4306-4316
Number of pages	11
Journal	European Journal of Inorganic Chemistry
Issue number	27
DOIs	https://doi.org/10.1002/ejic.200700419
State	Published - 2007

Keywords

Density functional calculations
Metal clusters
O ligands
Tungsten

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@article{a73e23f723f84924bd037d68d236393f,

title = "Aqueous reduction of [Cp*2W2O5]: Characterization of the triangular clusters [Cp*3W 3O4(OH)2]2+ and [Cp* 3W3O6]+ - Comparison with molybdenum",

abstract = "Zinc reduction of Cp*2W2O5 in an acidified water-methanol medium affords the green 3-electron trinuclear cluster [Cp*3W3O4(OH)2]2+, isolated and crystallographically characterized as the triflate salt, 1. Upon exposure to air, this complex is oxidized to a related 2-electron cluster, [Cp*3W3O6]+, which was crystallized and characterized in three different salts, 2-4. The 3-electron cluster exhibits a near-tetragonal frozen-glass EPR spectrum, and it shows evidence of coupling of the unpaired electron to only one of the three W atoms. The two-electron cluster is diamagnetic. An electrospray ionization MS n study revealed a stepwise expulsion of neutral [Cp*WO 2] units as the main fragmentation process. DFT calculations unveiled the intimate details of the electronic structures of these complexes and fully rationalized the structural and spectroscopic properties.",

keywords = "Density functional calculations, Metal clusters, O ligands, Tungsten",

author = "Chiara Dinoi and Pelin S{\"o}zen and G{\"u}lnur Taban and Deniz Demir and Funda Demirhan and Petr Prikhodchenko and Jenny Gun and Ovadia Lev and Daran, {Jean Claude} and Rinaldo Poli",

year = "2007",

doi = "10.1002/ejic.200700419",

language = "American English",

pages = "4306--4316",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "Wiley-VCH Verlag",

number = "27",

}

TY - JOUR

T1 - Aqueous reduction of [Cp*2W2O5]

T2 - Characterization of the triangular clusters [Cp*3W 3O4(OH)2]2+ and [Cp* 3W3O6]+ - Comparison with molybdenum

AU - Dinoi, Chiara

AU - Sözen, Pelin

AU - Taban, Gülnur

AU - Demir, Deniz

AU - Demirhan, Funda

AU - Prikhodchenko, Petr

AU - Gun, Jenny

AU - Lev, Ovadia

AU - Daran, Jean Claude

AU - Poli, Rinaldo

PY - 2007

Y1 - 2007

N2 - Zinc reduction of Cp*2W2O5 in an acidified water-methanol medium affords the green 3-electron trinuclear cluster [Cp*3W3O4(OH)2]2+, isolated and crystallographically characterized as the triflate salt, 1. Upon exposure to air, this complex is oxidized to a related 2-electron cluster, [Cp*3W3O6]+, which was crystallized and characterized in three different salts, 2-4. The 3-electron cluster exhibits a near-tetragonal frozen-glass EPR spectrum, and it shows evidence of coupling of the unpaired electron to only one of the three W atoms. The two-electron cluster is diamagnetic. An electrospray ionization MS n study revealed a stepwise expulsion of neutral [Cp*WO 2] units as the main fragmentation process. DFT calculations unveiled the intimate details of the electronic structures of these complexes and fully rationalized the structural and spectroscopic properties.

AB - Zinc reduction of Cp*2W2O5 in an acidified water-methanol medium affords the green 3-electron trinuclear cluster [Cp*3W3O4(OH)2]2+, isolated and crystallographically characterized as the triflate salt, 1. Upon exposure to air, this complex is oxidized to a related 2-electron cluster, [Cp*3W3O6]+, which was crystallized and characterized in three different salts, 2-4. The 3-electron cluster exhibits a near-tetragonal frozen-glass EPR spectrum, and it shows evidence of coupling of the unpaired electron to only one of the three W atoms. The two-electron cluster is diamagnetic. An electrospray ionization MS n study revealed a stepwise expulsion of neutral [Cp*WO 2] units as the main fragmentation process. DFT calculations unveiled the intimate details of the electronic structures of these complexes and fully rationalized the structural and spectroscopic properties.

KW - Density functional calculations

KW - Metal clusters

KW - O ligands

KW - Tungsten

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U2 - 10.1002/ejic.200700419

DO - 10.1002/ejic.200700419

M3 - Article

AN - SCOPUS:34948820124

SN - 1434-1948

SP - 4306

EP - 4316

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 27

ER -

Aqueous reduction of [Cp₂W₂O₅]: Characterization of the triangular clusters [Cp₃W ₃O₄(OH)₂]²⁺ and [Cp* ₃W₃O₆]⁺ - Comparison with molybdenum

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