Mono- and dinuclear high-spin half-sandwich manganese(II) complexes containing acetylide and TMEDA ligands

Sohrab Kheradmandan; Thomas Fox; Helmut W. Schmalle; Koushik Venkatesan; Heinz Berke

doi:10.1002/ejic.200400006

Mono- and dinuclear high-spin half-sandwich manganese(II) complexes containing acetylide and TMEDA ligands

Sohrab Kheradmandan, Thomas Fox, Helmut W. Schmalle, Koushik Venkatesan, Heinz Berke^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

20 Citations (Scopus)

Abstract

The d⁵ high-spin Mn^II half-sandwich complexes [Mn(C≡CR)(MeC₅H₄)(tmeda)] (R = SiMe₃ 2, Ph 3; tBu 4; C≡CSiMe₃ 5; C=CPh 6; tmeda = N,N,N′, N′-tetramethylethylenediamine) were prepared by the reaction of [Mn(MeC₅H₄)₂(tmeda)] (1) with 1 equiv. of the corresponding acetylene or the trimethyltin acetylide. The dinuclear complexes [Mn(C≡C-C≡CSiMe₃)₂(tmeda)]₂ (7) and [Mn₂-(MeCp)₂(μ₁-tBuC≡C) ₂(μ₁-tmeda)] (8), which contain Mn-Mn bonds, were synthesized by treating 1 with an excess of HC≡C-C≡CSiMe₃ or HC≡CtBu, respectively. Dinuclear complexes of the type [(MeC ₅H₄)(tmeda)MnC≡C-X-C≡CMn(tmeda)(C ₅H₄Me)] [X = 1,3-C₆H₄ 9; 1,4-C ₆H₄ 10; 4,4′-(C₆H₄) ₂ 11] were obtained by treatment of 1 with 0.5 equiv. of the corresponding acetylides 1,3-C₆H₄-(C≡CSnMe ₃)₂, 1,4-C₆H₄(C≡CSnMe ₃)₂ and 4,4′-(C₆H₄) ₂-(C≡CSnMe₃)₂ in benzene for 24 h to yield the corresponding dinuclear complexes in very good yields. All the mono- and dinuclear compounds have been characterized by NMR, IR, Raman spectroscopy and elemental analyses. X-ray diffraction studies have been performed on complexes 3 and 5-11.

Original language	English
Pages (from-to)	3544-3554
Number of pages	11
Journal	European Journal of Inorganic Chemistry
Issue number	17
DOIs	https://doi.org/10.1002/ejic.200400006
Publication status	Published - 6 Sept 2004
Externally published	Yes

Keywords

Alkyne ligands
Cyclopentadienyl ligands
Half-sandwich complexes
Molecular devices
N ligands

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10.1002/ejic.200400006

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@article{66a618898d144b51a868f2f542309da8,

title = "Mono- and dinuclear high-spin half-sandwich manganese(II) complexes containing acetylide and TMEDA ligands",

abstract = "The d5 high-spin MnII half-sandwich complexes [Mn(C≡CR)(MeC5H4)(tmeda)] (R = SiMe3 2, Ph 3; tBu 4; C≡CSiMe3 5; C=CPh 6; tmeda = N,N,N′, N′-tetramethylethylenediamine) were prepared by the reaction of [Mn(MeC5H4)2(tmeda)] (1) with 1 equiv. of the corresponding acetylene or the trimethyltin acetylide. The dinuclear complexes [Mn(C≡C-C≡CSiMe3)2(tmeda)]2 (7) and [Mn2-(MeCp)2(μ1-tBuC≡C) 2(μ1-tmeda)] (8), which contain Mn-Mn bonds, were synthesized by treating 1 with an excess of HC≡C-C≡CSiMe3 or HC≡CtBu, respectively. Dinuclear complexes of the type [(MeC 5H4)(tmeda)MnC≡C-X-C≡CMn(tmeda)(C 5H4Me)] [X = 1,3-C6H4 9; 1,4-C 6H4 10; 4,4′-(C6H4) 2 11] were obtained by treatment of 1 with 0.5 equiv. of the corresponding acetylides 1,3-C6H4-(C≡CSnMe 3)2, 1,4-C6H4(C≡CSnMe 3)2 and 4,4′-(C6H4) 2-(C≡CSnMe3)2 in benzene for 24 h to yield the corresponding dinuclear complexes in very good yields. All the mono- and dinuclear compounds have been characterized by NMR, IR, Raman spectroscopy and elemental analyses. X-ray diffraction studies have been performed on complexes 3 and 5-11.",

keywords = "Alkyne ligands, Cyclopentadienyl ligands, Half-sandwich complexes, Molecular devices, N ligands",

author = "Sohrab Kheradmandan and Thomas Fox and Schmalle, \{Helmut W.\} and Koushik Venkatesan and Heinz Berke",

year = "2004",

month = sep,

day = "6",

doi = "10.1002/ejic.200400006",

language = "English",

pages = "3544--3554",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "Wiley-VCH, Wiley",

number = "17",

}

TY - JOUR

T1 - Mono- and dinuclear high-spin half-sandwich manganese(II) complexes containing acetylide and TMEDA ligands

AU - Kheradmandan, Sohrab

AU - Fox, Thomas

AU - Schmalle, Helmut W.

AU - Venkatesan, Koushik

AU - Berke, Heinz

PY - 2004/9/6

Y1 - 2004/9/6

N2 - The d5 high-spin MnII half-sandwich complexes [Mn(C≡CR)(MeC5H4)(tmeda)] (R = SiMe3 2, Ph 3; tBu 4; C≡CSiMe3 5; C=CPh 6; tmeda = N,N,N′, N′-tetramethylethylenediamine) were prepared by the reaction of [Mn(MeC5H4)2(tmeda)] (1) with 1 equiv. of the corresponding acetylene or the trimethyltin acetylide. The dinuclear complexes [Mn(C≡C-C≡CSiMe3)2(tmeda)]2 (7) and [Mn2-(MeCp)2(μ1-tBuC≡C) 2(μ1-tmeda)] (8), which contain Mn-Mn bonds, were synthesized by treating 1 with an excess of HC≡C-C≡CSiMe3 or HC≡CtBu, respectively. Dinuclear complexes of the type [(MeC 5H4)(tmeda)MnC≡C-X-C≡CMn(tmeda)(C 5H4Me)] [X = 1,3-C6H4 9; 1,4-C 6H4 10; 4,4′-(C6H4) 2 11] were obtained by treatment of 1 with 0.5 equiv. of the corresponding acetylides 1,3-C6H4-(C≡CSnMe 3)2, 1,4-C6H4(C≡CSnMe 3)2 and 4,4′-(C6H4) 2-(C≡CSnMe3)2 in benzene for 24 h to yield the corresponding dinuclear complexes in very good yields. All the mono- and dinuclear compounds have been characterized by NMR, IR, Raman spectroscopy and elemental analyses. X-ray diffraction studies have been performed on complexes 3 and 5-11.

AB - The d5 high-spin MnII half-sandwich complexes [Mn(C≡CR)(MeC5H4)(tmeda)] (R = SiMe3 2, Ph 3; tBu 4; C≡CSiMe3 5; C=CPh 6; tmeda = N,N,N′, N′-tetramethylethylenediamine) were prepared by the reaction of [Mn(MeC5H4)2(tmeda)] (1) with 1 equiv. of the corresponding acetylene or the trimethyltin acetylide. The dinuclear complexes [Mn(C≡C-C≡CSiMe3)2(tmeda)]2 (7) and [Mn2-(MeCp)2(μ1-tBuC≡C) 2(μ1-tmeda)] (8), which contain Mn-Mn bonds, were synthesized by treating 1 with an excess of HC≡C-C≡CSiMe3 or HC≡CtBu, respectively. Dinuclear complexes of the type [(MeC 5H4)(tmeda)MnC≡C-X-C≡CMn(tmeda)(C 5H4Me)] [X = 1,3-C6H4 9; 1,4-C 6H4 10; 4,4′-(C6H4) 2 11] were obtained by treatment of 1 with 0.5 equiv. of the corresponding acetylides 1,3-C6H4-(C≡CSnMe 3)2, 1,4-C6H4(C≡CSnMe 3)2 and 4,4′-(C6H4) 2-(C≡CSnMe3)2 in benzene for 24 h to yield the corresponding dinuclear complexes in very good yields. All the mono- and dinuclear compounds have been characterized by NMR, IR, Raman spectroscopy and elemental analyses. X-ray diffraction studies have been performed on complexes 3 and 5-11.

KW - Alkyne ligands

KW - Cyclopentadienyl ligands

KW - Half-sandwich complexes

KW - Molecular devices

KW - N ligands

UR - https://www.scopus.com/pages/publications/4944235124

U2 - 10.1002/ejic.200400006

DO - 10.1002/ejic.200400006

M3 - Article

AN - SCOPUS:4944235124

SN - 1434-1948

SP - 3544

EP - 3554

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 17

ER -

Mono- and dinuclear high-spin half-sandwich manganese(II) complexes containing acetylide and TMEDA ligands

Abstract

Keywords

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