Alkali-metal-mediated manganation(II) of naphthalenes: constructing metal la-anthracene and metalla-phenanthrene structures

V.L. Blair, W. Clegg, R.E. Mulvey, L. 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 σ bonds to the deprotonated C atoms of the naphthyl ligands, whereas Na interacts with the aromatic π 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)2Na2(tmp)2(1,4-C6H4)Mn2(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.
LanguageEnglish
Pages8863-8870
Number of pages7
JournalInorganic Chemistry
Volume48
Issue number18
DOIs
Publication statusPublished - 21 Sep 2009

Fingerprint

Naphthalenes
Alkali Metals
phenanthrene
anthracene
naphthalene
alkali metals
Metals
Benzene
metals
Molecular structure
Crystal structure
Sodium
Impurities
Crystalline materials
Ligands
Atoms
Molecules
molecular structure
benzene
sodium

Keywords

  • Alkali-metal-mediated manganation
  • naphthalenes
  • metal la-anthracene
  • metalla-phenanthrene structures

Cite this

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title = "Alkali-metal-mediated manganation(II) of naphthalenes: constructing metal la-anthracene and metalla-phenanthrene structures",
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 σ bonds to the deprotonated C atoms of the naphthyl ligands, whereas Na interacts with the aromatic π 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)2Na2(tmp)2(1,4-C6H4)Mn2(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.",
keywords = "Alkali-metal-mediated manganation, naphthalenes, metal la-anthracene, metalla-phenanthrene structures",
author = "V.L. Blair and W. Clegg and R.E. Mulvey and L. Russo",
year = "2009",
month = "9",
day = "21",
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Alkali-metal-mediated manganation(II) of naphthalenes: constructing metal la-anthracene and metalla-phenanthrene structures. / Blair, V.L.; Clegg, W.; Mulvey, R.E.; Russo, L.

In: Inorganic Chemistry, Vol. 48, No. 18, 21.09.2009, p. 8863-8870.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Alkali-metal-mediated manganation(II) of naphthalenes: constructing metal la-anthracene and metalla-phenanthrene structures

AU - Blair, V.L.

AU - Clegg, W.

AU - Mulvey, R.E.

AU - Russo, L.

PY - 2009/9/21

Y1 - 2009/9/21

N2 - 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 σ bonds to the deprotonated C atoms of the naphthyl ligands, whereas Na interacts with the aromatic π 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)2Na2(tmp)2(1,4-C6H4)Mn2(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.

AB - 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 σ bonds to the deprotonated C atoms of the naphthyl ligands, whereas Na interacts with the aromatic π 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)2Na2(tmp)2(1,4-C6H4)Mn2(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.

KW - Alkali-metal-mediated manganation

KW - naphthalenes

KW - metal la-anthracene

KW - metalla-phenanthrene structures

UR - http://dx.doi.org/10.1021/ic901068w

U2 - 10.1021/ic901068w

DO - 10.1021/ic901068w

M3 - Article

VL - 48

SP - 8863

EP - 8870

JO - Inorganic Chemistry

T2 - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 18

ER -