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Alkali-Metal-Mediated Manganation(II) of Naphthalenes: Constructing Metal la-Anthracene and Metalla-Phenanthrene Structures

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

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Abstract

Alkali-metal-mediated manganation (AMMMn) reactions of the synergic base sodium monoalkyl-bisamidomanganate [(tmeda)Na(tmp)(CH2SiMe3)Mn(tmp)] (1) with naphthalene, 1-methoxynaphthalene, or 2-methoxynaphthalene are reported. These novel direct manganation [Mn(II)] reactions produced the crystalline ortho-manganated naphthyl products [(tmeda)Na(tmp)(2-C10H7)Mn(tmp)] (3), [(tmeda)Na(tmp){2-(1-MeOC10H6)}Mn(CH2SiMe3)] (4), and [(tmeda)Na-(tmp){3-(2-MeOC10H6)}Mn(tmp)] (5) in reasonable to good isolated yields of 88, 65, and 85%, respectively. All three new complexes have been crystallographically characterized, showing discrete molecular structures with trigonal planar Mn centers forming sigma bonds to the deprotonated C atoms of the naphthyl ligands, whereas Na interacts with the aromatic pi system in 3 or with the MeO substituent in 4 and 5. These latter interactions lead to interesting 5,6,7,8-tetrahydrophenanthrene-like and 1,2,3,4-tetrahydroanthracene-like metallacyclic motifs in 4 and 5, respectively. The sensitivity of these AMMMn reactions to impurities has been illustrated in the serendipitous preparation of the benzenediide complex [(tmeda)(2)Na-2(tmp)(2)(1,4-C6H4)Mn-2(tmp)(2)] (6) from one attempted repeat synthesis of 5. An "open inverse crown" arrangement with a 1,4-dimanganated benzene molecule is revealed in the crystal structure of 6.


Publication metadata

Author(s): Blair VL, Clegg W, Mulvey RE, Russo L

Publication type: Article

Publication status: Published

Journal: Inorganic Chemistry

Year: 2009

Volume: 48

Issue: 18

Pages: 8863-8870

ISSN (print): 0020-1669

ISSN (electronic): 1520-510X

Publisher: American Chemical Society

URL: http://dx.doi.org/10.1021/ic901068w

DOI: 10.1021/ic901068w


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