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Synthesis and structure of nickel-containing cuboidal clusters derived from [W3Se4(H2O)9]4+. Site-differentiated substitution at the nickel site in the series [W 3NiQ4(H2O)10]4+ (Q = S, Se)

Lookup NU author(s): Dr Maxim Sokolov, Emeritus Professor Bill Clegg

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Abstract

New Ni-containing heterometallic cuboidal cluster aqua complex [W 3(NiCl)Se4(H2O)9]3+, the missing link in the family of the M3NiQ4 clusters (M = Mo, W; Q = S, Se), has been prepared by the reaction of [W3Se 4(H2O)9]4+ with Ni in 2 M HCl. Single crystals of edge-linked double-cuboidal cluster [{W3NiSe 4(H2O)9}2](pts)8· 18H2O (pts = p-toluenesulfonate) were grown from the solution of the aqua complex in 3 M Hpts, and their structures were determined. The Ni site in the clusters [W3(NiCl)Q4(H2O)9] 3+ selectively coordinates typical π-acceptor ligands such as CO, olefins, acetylenes, phosphines, arsines, or SnCl3-. This allows stabilization by coordination of such elusive species as HP(OH) 2 and As(OH)3. The stability constants for coordination of HP(OH)2, As(OH)3, and SnCl3- were determined. The Se for S substitution increases the stability by 1-2 orders of magnitude. Supramolecular adducts with cucurbit[6]uril (Cuc), [W 3(Ni(HP(OH)2))Q4(H2O) 9]Cl4·Cuc·11H2O and [W 3(NiAs(OH)3)S4(H2O) 8Cl]Cl3·Cuc·13H2O, were isolated and structurally characterized. © 2006 American Chemical Society.


Publication metadata

Author(s): Hernandez-Molina R, Sokolov MN, Clausen M, Clegg W

Publication type: Article

Publication status: Published

Journal: Inorganic Chemistry

Year: 2006

Volume: 45

Issue: 26

Pages: 10567-10575

ISSN (print): 0020-1669

ISSN (electronic): 1520-510X

Publisher: American Chemical Society

URL: http://dx.doi.org/10.1021/ic061146n

DOI: 10.1021/ic061146n


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