Bis[(trimethylsilyl)methyl]manganese: structural variations of its solvent-free and tmeda-, pyridine-, and dioxane-complexed forms

A. Alberola, V.L. Blair, L.M. Carrella, W. Clegg, A.R. Kennedy, J. Klett, R.E. Mulvey, S. Newton

Research output: Contribution to journalArticle

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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.
LanguageEnglish
Pages2112-2118
Number of pages6
JournalOrganometallics
Volume28
Issue number7
DOIs
Publication statusPublished - 13 Apr 2009

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Manganese
infinity
manganese
pyridines
Lewis Bases
Lewis base
Manganese compounds
Alkali Metals
manganese ions
Atoms
Exchange coupling
spin exchange
X ray crystallography
Magnetic variables measurement
Bond length
alkali metals
crystallography
magnetic measurement
atoms
Polymers

Keywords

  • manganese(ii) dialkyls
  • crystal-structure
  • polymerization
  • adducts
  • bridges

Cite this

Alberola, A. ; Blair, V.L. ; Carrella, L.M. ; Clegg, W. ; Kennedy, A.R. ; Klett, J. ; Mulvey, R.E. ; Newton, S. / Bis[(trimethylsilyl)methyl]manganese: structural variations of its solvent-free and tmeda-, pyridine-, and dioxane-complexed forms. In: Organometallics. 2009 ; Vol. 28, No. 7. pp. 2112-2118.
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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.",
keywords = "manganese(ii) dialkyls, crystal-structure, polymerization, adducts, bridges",
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Bis[(trimethylsilyl)methyl]manganese: structural variations of its solvent-free and tmeda-, pyridine-, and dioxane-complexed forms. / Alberola, A.; Blair, V.L.; Carrella, L.M.; Clegg, W.; Kennedy, A.R.; Klett, J.; Mulvey, R.E.; Newton, S.

In: Organometallics, Vol. 28, No. 7, 13.04.2009, p. 2112-2118.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Bis[(trimethylsilyl)methyl]manganese: structural variations of its solvent-free and tmeda-, pyridine-, and dioxane-complexed forms

AU - Alberola, A.

AU - Blair, V.L.

AU - Carrella, L.M.

AU - Clegg, W.

AU - Kennedy, A.R.

AU - Klett, J.

AU - Mulvey, R.E.

AU - Newton, S.

N1 - Strathprints' policy is to record up to 8 authors per publication, plus any additional authors based at the University of Strathclyde. More authors may be listed on the official publication than appear in the Strathprints' record.

PY - 2009/4/13

Y1 - 2009/4/13

N2 - 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.

AB - 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.

KW - manganese(ii) dialkyls

KW - crystal-structure

KW - polymerization

KW - adducts

KW - bridges

UR - http://dx.doi.org/10.1021/om801135d

U2 - 10.1021/om801135d

DO - 10.1021/om801135d

M3 - Article

VL - 28

SP - 2112

EP - 2118

JO - Organometallics

T2 - Organometallics

JF - Organometallics

SN - 0276-7333

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ER -