Synthesis, structure, and reactivity of novel iron(II) complexes with a five-membered chelate ligand κ                         2                         (Si,N)- SiMe                         2                         O(2-C                         5                         H                         4                         N)

Takahiro Sato; Masaaki Okazaki; Hiromi Tobita; Hiroshi Ogino

doi:10.1016/S0022-328X(03)00043-3

Synthesis, structure, and reactivity of novel iron(II) complexes with a five-membered chelate ligand κ ² (Si,N)- SiMe ₂ O(2-C ₅ H ₄ N)

Takahiro Sato, Masaaki Okazaki, Hiromi Tobita, Hiroshi Ogino

Institute for Excellence in Higher Education (IEHE) (organization affiliation only)

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

13 Citations (Scopus)

Abstract

Photolysis of Cp′(CO) ₂ FeSiMe ₂ O (2-C ₅ H ₄ N) (1a: Cp′ = η ⁵ - C ₅ H ₅ (Cp), 1b: Cp′ = η ⁵ -C ₅ Me ₅ (Cp*)) afforded Cp′(CO)Fe[κ ² (Si,N)-SiMe ₂ O(2-C ₅ H ₄ N)] (2a: Cp′ = Cp, 2b: Cp′ = Cp*) in good yield each. These cyclic compounds also formed in moderate yields through photoreaction of Cp′ (CO) ₂ FeSiMe ₃ with HSiMe ₂ O(2-C ₅ H ₄ N) (3). Single-crystal X-ray diffraction study confirmed the structure of 2b containing a five-membered chelate ring comprised of Fe, Si, O, C, and N. Complexes 2a and 2b were thermally stable and did not react with slight excess of PR ₃ (R = Me, Ph) in benzene-d ₆ solution below 80 °C. Above 80 °C, 2a reacted slowly with PR ₃ to give Cp(CO)(PR ₃ )FeSiMe ₂ O (2-C ₅ H ₄ N) (6: R = Me, 7: R = Ph) accompanied by the cleavage of the Fe-N bond. These results indicate that both Fe-Si bond and Fe-N bond in 2 are notably sturdy.

Original language	English
Pages (from-to)	189-199
Number of pages	11
Journal	Journal of Organometallic Chemistry
Volume	669
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(03)00043-3
Publication status	Published - 2003 Mar 3

Keywords

Chelate
Iron complexes
Photolysis
Silyl complexes
X-ray structure analysis

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/S0022-328X(03)00043-3

Cite this

Sato, T., Okazaki, M., Tobita, H., & Ogino, H. (2003). Synthesis, structure, and reactivity of novel iron(II) complexes with a five-membered chelate ligand κ ² (Si,N)- SiMe ₂ O(2-C ₅ H ₄ N) Journal of Organometallic Chemistry, 669(1-2), 189-199. https://doi.org/10.1016/S0022-328X(03)00043-3

Synthesis, structure, and reactivity of novel iron(II) complexes with a five-membered chelate ligand κ ² (Si,N)- SiMe ₂ O(2-C ₅ H ₄ N) . / Sato, Takahiro; Okazaki, Masaaki; Tobita, Hiromi et al.

In: Journal of Organometallic Chemistry, Vol. 669, No. 1-2, 03.03.2003, p. 189-199.

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

Sato, T, Okazaki, M, Tobita, H & Ogino, H 2003, ' Synthesis, structure, and reactivity of novel iron(II) complexes with a five-membered chelate ligand κ ² (Si,N)- SiMe ₂ O(2-C ₅ H ₄ N) ', Journal of Organometallic Chemistry, vol. 669, no. 1-2, pp. 189-199. https://doi.org/10.1016/S0022-328X(03)00043-3

Sato T, Okazaki M, Tobita H, Ogino H. Synthesis, structure, and reactivity of novel iron(II) complexes with a five-membered chelate ligand κ ² (Si,N)- SiMe ₂ O(2-C ₅ H ₄ N) Journal of Organometallic Chemistry. 2003 Mar 3;669(1-2):189-199. doi: 10.1016/S0022-328X(03)00043-3

Sato, Takahiro ; Okazaki, Masaaki ; Tobita, Hiromi et al. / Synthesis, structure, and reactivity of novel iron(II) complexes with a five-membered chelate ligand κ ² (Si,N)- SiMe ₂ O(2-C ₅ H ₄ N) In: Journal of Organometallic Chemistry. 2003 ; Vol. 669, No. 1-2. pp. 189-199.

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title = " Synthesis, structure, and reactivity of novel iron(II) complexes with a five-membered chelate ligand κ 2 (Si,N)- SiMe 2 O(2-C 5 H 4 N) ",

abstract = " Photolysis of Cp′(CO) 2 FeSiMe 2 O (2-C 5 H 4 N) (1a: Cp′ = η 5 - C 5 H 5 (Cp), 1b: Cp′ = η 5 -C 5 Me 5 (Cp*)) afforded Cp′(CO)Fe[κ 2 (Si,N)-SiMe 2 O(2-C 5 H 4 N)] (2a: Cp′ = Cp, 2b: Cp′ = Cp*) in good yield each. These cyclic compounds also formed in moderate yields through photoreaction of Cp′ (CO) 2 FeSiMe 3 with HSiMe 2 O(2-C 5 H 4 N) (3). Single-crystal X-ray diffraction study confirmed the structure of 2b containing a five-membered chelate ring comprised of Fe, Si, O, C, and N. Complexes 2a and 2b were thermally stable and did not react with slight excess of PR 3 (R = Me, Ph) in benzene-d 6 solution below 80 °C. Above 80 °C, 2a reacted slowly with PR 3 to give Cp(CO)(PR 3 )FeSiMe 2 O (2-C 5 H 4 N) (6: R = Me, 7: R = Ph) accompanied by the cleavage of the Fe-N bond. These results indicate that both Fe-Si bond and Fe-N bond in 2 are notably sturdy.",

keywords = "Chelate, Iron complexes, Photolysis, Silyl complexes, X-ray structure analysis",

author = "Takahiro Sato and Masaaki Okazaki and Hiromi Tobita and Hiroshi Ogino",

note = "Funding Information: This work was supported by a Grant-in-Aid for Scientific Research (No. 14204065) and by Grants-in-Aid for Scientific Research on Priority Areas (Nos. 4078202 and 14044010) from the Ministry of Education, Culture, Sports, Science and Technology, Japan. We thank Dow Corning Toray Silicone Co., Ltd. and Shin-Etsu Chemical Co. Ltd., for gifts of silicon compounds.",

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T1 - Synthesis, structure, and reactivity of novel iron(II) complexes with a five-membered chelate ligand κ 2 (Si,N)- SiMe 2 O(2-C 5 H 4 N)

AU - Sato, Takahiro

AU - Okazaki, Masaaki

AU - Tobita, Hiromi

AU - Ogino, Hiroshi

N1 - Funding Information: This work was supported by a Grant-in-Aid for Scientific Research (No. 14204065) and by Grants-in-Aid for Scientific Research on Priority Areas (Nos. 4078202 and 14044010) from the Ministry of Education, Culture, Sports, Science and Technology, Japan. We thank Dow Corning Toray Silicone Co., Ltd. and Shin-Etsu Chemical Co. Ltd., for gifts of silicon compounds.

PY - 2003/3/3

Y1 - 2003/3/3

N2 - Photolysis of Cp′(CO) 2 FeSiMe 2 O (2-C 5 H 4 N) (1a: Cp′ = η 5 - C 5 H 5 (Cp), 1b: Cp′ = η 5 -C 5 Me 5 (Cp*)) afforded Cp′(CO)Fe[κ 2 (Si,N)-SiMe 2 O(2-C 5 H 4 N)] (2a: Cp′ = Cp, 2b: Cp′ = Cp*) in good yield each. These cyclic compounds also formed in moderate yields through photoreaction of Cp′ (CO) 2 FeSiMe 3 with HSiMe 2 O(2-C 5 H 4 N) (3). Single-crystal X-ray diffraction study confirmed the structure of 2b containing a five-membered chelate ring comprised of Fe, Si, O, C, and N. Complexes 2a and 2b were thermally stable and did not react with slight excess of PR 3 (R = Me, Ph) in benzene-d 6 solution below 80 °C. Above 80 °C, 2a reacted slowly with PR 3 to give Cp(CO)(PR 3 )FeSiMe 2 O (2-C 5 H 4 N) (6: R = Me, 7: R = Ph) accompanied by the cleavage of the Fe-N bond. These results indicate that both Fe-Si bond and Fe-N bond in 2 are notably sturdy.

AB - Photolysis of Cp′(CO) 2 FeSiMe 2 O (2-C 5 H 4 N) (1a: Cp′ = η 5 - C 5 H 5 (Cp), 1b: Cp′ = η 5 -C 5 Me 5 (Cp*)) afforded Cp′(CO)Fe[κ 2 (Si,N)-SiMe 2 O(2-C 5 H 4 N)] (2a: Cp′ = Cp, 2b: Cp′ = Cp*) in good yield each. These cyclic compounds also formed in moderate yields through photoreaction of Cp′ (CO) 2 FeSiMe 3 with HSiMe 2 O(2-C 5 H 4 N) (3). Single-crystal X-ray diffraction study confirmed the structure of 2b containing a five-membered chelate ring comprised of Fe, Si, O, C, and N. Complexes 2a and 2b were thermally stable and did not react with slight excess of PR 3 (R = Me, Ph) in benzene-d 6 solution below 80 °C. Above 80 °C, 2a reacted slowly with PR 3 to give Cp(CO)(PR 3 )FeSiMe 2 O (2-C 5 H 4 N) (6: R = Me, 7: R = Ph) accompanied by the cleavage of the Fe-N bond. These results indicate that both Fe-Si bond and Fe-N bond in 2 are notably sturdy.

KW - Chelate

KW - Iron complexes

KW - Photolysis

KW - Silyl complexes

KW - X-ray structure analysis

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