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