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Highly Reduced, Polyoxo(alkoxo)vanadium(III/IV) Clusters
Author(s) -
Tidmarsh Ian S.,
Laye Rebecca H.,
Brearley Paul R.,
Shanmugam Maheswaran,
Sañudo E. Carolina,
Sorace Lorenzo,
Caneschi Andrea,
McInnes Eric J. L.
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200700247
Subject(s) - vanadium , chemistry , crystallization , oxidation state , crystallography , crystal structure , medicinal chemistry , solid state , stereochemistry , inorganic chemistry , catalysis , organic chemistry
A family of high nuclearity oxo(alkoxo)vanadium clusters in unprecedentedly low oxidation states is reported, synthesised from simple vanadium diketonate precursors in alcohols under solvothermal conditions. Crystal structures of [V 18 (O) 12 (OH) 2 (H 2 O) 4 (EtO) 22 (O 2 CPh) 6 (acac) 2 ] ( 1 ), [V 16 Na 2 (O) 18 (EtO) 16 (EtOH) 2 (O 2 CPh) 6 (HO 2 CPh) 2 ] ∞ ( 2 ), [V 13 (O) 13 (EtO) 15 (EtOH)(RCO 2 ) 3 ] in which R=adamantyl ( 3 ) or Ph 3 C ( 4 ), and [V 11 (O) 12 (EtO) 13 (EtOH)(Ph 3 CCO 2 ) 2 (MePO 3 )] ( 5 ) are reported, revealing these to be {V III 16 V IV 2 } ( 1 ), {V III 9 V IV 3 V V } ( 3 and 4 ) and {V III 3 V IV 8 } ( 5 ) clusters, while 2 consists of isolated {V III 8 V IV 8 } clusters bridged into polymeric chains by {Na 2 (OEt) 2 } fragments. Solvothermal conditions are essential to the formation of these species, and the level of oxidation of the isolated clusters is in part controlled by the crystallisation time, with the lowest mean‐oxidation‐state species being isolated by direct crystallisation on controlled cooling of the reaction solutions.