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Issue 8, 2006
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Synthesis and structural characterization of scandium SALEN complexes

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Abstract

A series of heteroleptic scandium SALEN complexes, [(SALEN)Sc(µ-Cl)]2 and (SALEN)Sc[N(SiHMe2)2] is obtained via amine elimination reactions using [Sc(NiPr2)2(µ-Cl)(THF)]2 and Sc[N(SiHMe2)2]3(THF) as metal precursors, respectively. H2SALEN ligand precursors comprising H2Salen [(1,2-ethandiyl)bis(nitrilomethylidyne)bis(2,4-di-tert-butyl)phenol], H2Salpren [(2,2-dimethylpropanediyl)bis(nitrilomethylidyne)bis(2,4-di-tert-butyl)phenol], H2Salcyc [(1R,2R)-(−)-1,2-cyclohexanediyl)bis(nitrilomethylidyne)bis(2,4-di-tert-butyl)phenol] and H2Salphen [((1S,2S)-(−)-1,2-diphenylethandiyl)bis(nitrilomethylidyne)bis(2,4-di-tert-butyl)phenol] are selected according to solubility and ligand backbone variation (“[double bond, length as m-dash]N–(R)–N[double bond, length as m-dash]” bite angle) criteria. Consideration is given to the feasibility of [Cl → NR2] and [N(SiHMe2)2 → OSiR3] secondary ligand exchange reactions. X-ray crystal structure analyses of donor-free (Salpren)Sc(NiPr2), (R,R)-(Salcyc)Sc[N(SiHMe2)2], (Salen)Sc(OSitBuPh2) and (Salphen)Sc(OSiHtBu2) reveal (i) a very short Sc–N bond distance of 2.000(3) Å, (ii) weak β(Si–H)amido–Sc agostic interactions and (iii) an exclusive intramolecularly tetradentate and intrinsically bent coordination mode of the SALEN ligands with ∠(Ph,Ph) dihedral angles and Sc–[N2O2] distances in the 124.27(9)–127.7(3)° and 0.638(1)–0.688(1) Å range, respectively.

Graphical abstract: Synthesis and structural characterization of scandium SALEN complexes

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Supplementary files

Article information


Submitted
20 Sep 2005
Accepted
09 Nov 2005
First published
14 Dec 2005

Dalton Trans., 2006, 1041-1050
Article type
Paper

Synthesis and structural characterization of scandium SALEN complexes

C. Meermann, P. Sirsch, K. W. Törnroos and R. Anwander, Dalton Trans., 2006, 1041
DOI: 10.1039/B513370J

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