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Bis[(trimethylsilyl)methyl]manganese: Structural Variations of Its Solvent-Free and TMEDA-, Pyridine-, and Dioxane-Complexed Forms

Lookup NU author(s): Professor William Clegg, Dr Luca Russo

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Abstract

First synthesized in 1976 and recently taking on a new significance as a key precursor to heterobimetallic alkali-metal-manganese(II) complexes, bis[(trimethylsilyl)methyl] manganese has been structurally characterized by X-ray crystallography. It forms a polymeric chain structure of formula [{Mn(CH2SiMe3)(2)}(infinity)], 1, in which distorted tetrahedral, spiro Mn atoms are linked together via mu(2)-bonding alkyl ligands. The structure is notable for displaying two distinct categories of Mn-C bond lengths with a mean size differential of 0.225 angstrom and for being the first fully crystallographically characterized polymeric manganese(II) dialkyl compound. Magnetic measurements of 1 indicate a surprisingly strong spin exchange coupling of J approximate to -45 cm(-1) between the manganese ions aligned along the chain. Four Lewis base complexes of bis[(trimethyl silyl)methyl] manganese have also been subjected to X-ray crystallographic studies. Previously known [TMEDA center dot Mn(CH2SiMe3)(2)], 2, and [(pyridine)(2)Mn(CH2SiMe3)(2)], 3, both adopt a simple monomeric arrangement with C2N2 distorted tetrahedral coordinations of the metal atom. Synthesized by direct addition of the Lewis base to 1, two further, new complexes, [{(dioxane)-[Mn(CH2SiMe3)(2)](2)}(infinity)], 4, and [{(dioxane)[Mn(CH2SiMe3)(2)]}(infinity)], 5, are also reported. Hemisolvate 4 displays dimeric [(Me3SiCH2)Mn(mu-CH2SiMe3)(2)Mn(CH2SiMe3)] subunits, whereas 1:1 solvate 5 consists of monomeric subunits of [{Mn(CH2SiMe3)(2)}(infinity)]; in both cases these subunits are linked together via O(CH2CH2)(2)O bridges to generate one-dimensional polymers.

Publication metadata

Author(s): Alberola A, Blair VL, Carrella LM, Clegg W, Kennedy AR, Klett J, Mulvey RE, Newton S, Rentschler E, Russo L

Publication type: Article

Publication status: Published

Journal: Organometallics

Year: 2009

Volume: 28

Issue: 7

Pages: 2112-2118

ISSN (print): 0276-7333

ISSN (electronic): 1520-6041

Publisher: American Chemical Society

URL: http://dx.doi.org/10.1021/om801135d

DOI: 10.1021/om801135d

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