Aqueous Reduction of [Cp* 2 W 2 O 5 ]: Characterization of the Triangular Clusters [Cp* 3 W 3 O 4 (OH) 2 ] 2+  and [Cp* 3 W 3 O 6 ] +  – Comparison with Molybdenum | Zendy

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

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Aqueous Reduction of [Cp* 2 W 2 O 5 ]: Characterization of the Triangular Clusters [Cp* 3 W 3 O 4 (OH) 2 ] 2+ and [Cp* 3 W 3 O 6 ] + – Comparison with Molybdenum

Author(s) -

Dinoi Chiara,

Sözen Pelin,

Taban Gülnur,

Demir Deniz,

Demirhan Funda,

Prikhodchenko Petr,

Gun Jenny,

Lev Ovadia,

Daran JeanClaude,

Poli Rinaldo

Publication year - 2007

Publication title -

european journal of inorganic chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 0.667

H-Index - 136

eISSN - 1099-0682

pISSN - 1434-1948

DOI - 10.1002/ejic.200700419

Subject(s) - chemistry , electron paramagnetic resonance , crystallography , unpaired electron , polyoxometalate , cluster (spacecraft) , tetragonal crystal system , aqueous solution , diamagnetism , zinc , one electron reduction , inorganic chemistry , analytical chemistry (journal) , crystal structure , molecule , nuclear magnetic resonance , electrochemistry , biochemistry , physics , organic chemistry , quantum mechanics , electrode , computer science , magnetic field , programming language , catalysis , chromatography

Zinc reduction of Cp* 2 W 2 O 5 in an acidified water–methanol medium affords the green 3‐electron trinuclear cluster [Cp* 3 W 3 O 4 (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* 3 W 3 O 6 ] + , 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.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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