Highly reduced, polyoxo(alkoxo)vanadium(IIII/IV) clusters

Ian S. Tidmarsh; Rebecca H. Laye; Paul R. Brearley; Maheswaran Shanmugam; E. Carolina Sañudo; Lorenzo Sorace; Andrea Caneschi; Eric J L McInnes

doi:10.1002/chem.200700247

Highly reduced, polyoxo(alkoxo)vanadium(IIII/IV) clusters

Ian S. Tidmarsh, Rebecca H. Laye, Paul R. Brearley, Maheswaran Shanmugam, E. Carolina Sañudo, Lorenzo Sorace, Andrea Caneschi, Eric J L McInnes

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

Abstract

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 [V18(O)12(OH)2-(H2O) 4(EtO)22(O2CPh)6(acac)2] (1), [V16Na2(O)18(EtO)16(EtOH) 2(O2CPh)6-(HO2CPh)2] ∞ (2), [V13(O)13(EtO)15-(EtOH) (RCO2)3] in which R = adamantyl (3) or Ph3C (4), and [V11(O)12-(EtO)13(EtOH)(Ph 3CCO2)2(MePO3)] (5) are reported, revealing these to be (VIII16VIV2} (1), {VIII9V1V3VV) (3 and 4) and {VIII3VIV8} (5) clusters, while 2 consists of isolated {VIII8VIV 8} clusters bridged into polymeric chains by (Na2-(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. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.

Original language	English
Pages (from-to)	6329-6338
Number of pages	9
Journal	Chemistry - A European Journal
Volume	13
Issue number	22
DOIs	https://doi.org/10.1002/chem.200700247
Publication status	Published - 2007

Keywords

Cluster compounds
Polyoxometalates
Solvothermal synthesis
Vanadium

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10.1002/chem.200700247

CCDC 636596: Experimental Crystal Structure Determination
Tidmarsh, I. S. (Contributor), Laye, R. H. (Contributor), Brearley, P. R. (Contributor), Shanmugam, M. (Contributor), Sañudo, E. C. (Contributor), Sorace, L. (Contributor), Caneschi, A. (Contributor) & Mcinnes, E. (Contributor), Cambridge Crystallographic Data Centre, 9 Feb 2007
DOI: 10.5517/ccpcfct, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccpcfct&sid=DataCite
Dataset
CCDC 299653: Experimental Crystal Structure Determination
Tidmarsh, I. S. (Contributor), Laye, R. H. (Contributor), Brearley, P. R. (Contributor), Shanmugam, M. (Contributor), Sañudo, E. C. (Contributor), Sorace, L. (Contributor), Caneschi, A. (Contributor) & Mcinnes, E. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2006
DOI: 10.5517/ccb1t7d, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccb1t7d&sid=DataCite
Dataset
CCDC 636595: Experimental Crystal Structure Determination
Tidmarsh, I. S. (Contributor), Laye, R. H. (Contributor), Brearley, P. R. (Contributor), Shanmugam, M. (Contributor), Sañudo, E. C. (Contributor), Sorace, L. (Contributor), Caneschi, A. (Contributor) & Mcinnes, E. (Contributor), Cambridge Crystallographic Data Centre, 9 Feb 2007
DOI: 10.5517/ccpcfbs, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccpcfbs&sid=DataCite
Dataset

Cite this

@article{02ef5a091dc3444b9ed0e4092ee21784,

title = "Highly reduced, polyoxo(alkoxo)vanadium(IIII/IV) clusters",

abstract = "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 [V18(O)12(OH)2-(H2O) 4(EtO)22(O2CPh)6(acac)2] (1), [V16Na2(O)18(EtO)16(EtOH) 2(O2CPh)6-(HO2CPh)2] ∞ (2), [V13(O)13(EtO)15-(EtOH) (RCO2)3] in which R = adamantyl (3) or Ph3C (4), and [V11(O)12-(EtO)13(EtOH)(Ph 3CCO2)2(MePO3)] (5) are reported, revealing these to be (VIII16VIV2} (1), {VIII9V1V3VV) (3 and 4) and {VIII3VIV8} (5) clusters, while 2 consists of isolated {VIII8VIV 8} clusters bridged into polymeric chains by (Na2-(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. {\textcopyright} 2007 Wiley-VCH Verlag GmbH & Co. KGaA.",

keywords = "Cluster compounds, Polyoxometalates, Solvothermal synthesis, Vanadium",

author = "Tidmarsh, {Ian S.} and Laye, {Rebecca H.} and Brearley, {Paul R.} and Maheswaran Shanmugam and Sa{\~n}udo, {E. Carolina} and Lorenzo Sorace and Andrea Caneschi and McInnes, {Eric J L}",

year = "2007",

doi = "10.1002/chem.200700247",

language = "English",

volume = "13",

pages = "6329--6338",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley & Sons Ltd",

number = "22",

}

TY - JOUR

T1 - Highly reduced, polyoxo(alkoxo)vanadium(IIII/IV) clusters

AU - Tidmarsh, Ian S.

AU - Laye, Rebecca H.

AU - Brearley, Paul R.

AU - Shanmugam, Maheswaran

AU - Sañudo, E. Carolina

AU - Sorace, Lorenzo

AU - Caneschi, Andrea

AU - McInnes, Eric J L

PY - 2007

Y1 - 2007

N2 - 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 [V18(O)12(OH)2-(H2O) 4(EtO)22(O2CPh)6(acac)2] (1), [V16Na2(O)18(EtO)16(EtOH) 2(O2CPh)6-(HO2CPh)2] ∞ (2), [V13(O)13(EtO)15-(EtOH) (RCO2)3] in which R = adamantyl (3) or Ph3C (4), and [V11(O)12-(EtO)13(EtOH)(Ph 3CCO2)2(MePO3)] (5) are reported, revealing these to be (VIII16VIV2} (1), {VIII9V1V3VV) (3 and 4) and {VIII3VIV8} (5) clusters, while 2 consists of isolated {VIII8VIV 8} clusters bridged into polymeric chains by (Na2-(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. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.

AB - 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 [V18(O)12(OH)2-(H2O) 4(EtO)22(O2CPh)6(acac)2] (1), [V16Na2(O)18(EtO)16(EtOH) 2(O2CPh)6-(HO2CPh)2] ∞ (2), [V13(O)13(EtO)15-(EtOH) (RCO2)3] in which R = adamantyl (3) or Ph3C (4), and [V11(O)12-(EtO)13(EtOH)(Ph 3CCO2)2(MePO3)] (5) are reported, revealing these to be (VIII16VIV2} (1), {VIII9V1V3VV) (3 and 4) and {VIII3VIV8} (5) clusters, while 2 consists of isolated {VIII8VIV 8} clusters bridged into polymeric chains by (Na2-(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. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.

KW - Cluster compounds

KW - Polyoxometalates

KW - Solvothermal synthesis

KW - Vanadium

U2 - 10.1002/chem.200700247

DO - 10.1002/chem.200700247

M3 - Article

SN - 0947-6539

VL - 13

SP - 6329

EP - 6338

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 22

ER -

Highly reduced, polyoxo(alkoxo)vanadium(IIII/IV) clusters

Abstract

Keywords

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Datasets

CCDC 636596: Experimental Crystal Structure Determination

CCDC 299653: Experimental Crystal Structure Determination

CCDC 636595: Experimental Crystal Structure Determination

Cite this