Redistribution reactions of hydrosilanes mediated by the unsymmetrical and homometallic phosphido-bridged complex (η
                        5
                        -C
                        5
                        Me
                        5
                        )Fe
                        2
                        (CO)
                        4
                        ( μ-CO)(μ-PPh
                        2
                        )

Hisako Hashimoto; Hiromi Tobita; Hiroshi Ogino

doi:10.1016/0022-328X(95)00301-6

Redistribution reactions of hydrosilanes mediated by the unsymmetrical and homometallic phosphido-bridged complex (η ⁵ -C ₅ Me ₅ )Fe ₂ (CO) ₄ ( μ-CO)(μ-PPh ₂ )

Hisako Hashimoto, Hiromi Tobita, Hiroshi Ogino

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

28 Citations (Scopus)

Abstract

Reactions of the unsymmetrical and homobimetallic phosphido-bridged complex (η ⁵ -C ₅ Me ₅ )Fe ₂ (CO) ₄ (μ-CO)(μ-PPh ₂ ) (1) with various hydrosilanes gave rise to redistribution of the substituents on hydrosilanes. The reaction of 1 with 2 equiv. of secondary silane R ₂ SiH ₂ (R = Ph, p-Tol) caused effective aryl scrambling to afford a monoarylsilylene-bridged complex (η ⁵ -C ₅ Me ₅ )Fe ₂ (CO) ₄ (μ-SiRH)(μ-PPh ₂ ) (2, R = Ph; 3, R = p-Tol) and a tertiary silane R ₃ SiH (R = Ph, p-Tol). The signals of ²⁹ Si and ³¹ P ¹ H NMR spectra of these complexes appear at very low field ( ²⁹ Si NMR; 2, δ 209.1, ¹ J(SiH) = 185 Hz, ² J(SiP) = 26 Hz; 3, δ 209.1 ¹ J(SiH) = 185 Hz, ² J(SiP) = 27 Hz. ³¹ P NMR: 2, δ 224.5: 3, δ 225.0). Complex 2 and Ph ₃ SiH were also formed by the reaction of 1 with 1 equiv. of dihydrodisilane HPh ₂ SiSiPh ₂ H. Similarly, the reaction of 1 with alkyldisilane HMe ₂ SiSiMe ₂ H proceeded smoothly to give the alkyl-scrambling product (η ⁵ -C ₅ Me ₅ )Fe ₂ (CO) ₄ (μ-SiMeH)(μ-PPh ₂ ) (4) and Me ₃ SiH. Some intermediates were observed in each reaction by NMR spectroscopy. A reaction mechanism containing silyl(silylene) intermediates is proposed.

Original language	English
Pages (from-to)	205-211
Number of pages	7
Journal	Journal of Organometallic Chemistry
Volume	499
Issue number	1-2
DOIs	https://doi.org/10.1016/0022-328X(95)00301-6
Publication status	Published - 1995 Sept 6

Keywords

Carbonyl
Cyclopentadienyl
Iron
Phosphorus
Silane
Silylene

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/0022-328X(95)00301-6

Cite this

Hashimoto, H., Tobita, H., & Ogino, H. (1995). Redistribution reactions of hydrosilanes mediated by the unsymmetrical and homometallic phosphido-bridged complex (η ⁵ -C ₅ Me ₅ )Fe ₂ (CO) ₄ ( μ-CO)(μ-PPh ₂ ) Journal of Organometallic Chemistry, 499(1-2), 205-211. https://doi.org/10.1016/0022-328X(95)00301-6

Redistribution reactions of hydrosilanes mediated by the unsymmetrical and homometallic phosphido-bridged complex (η ⁵ -C ₅ Me ₅ )Fe ₂ (CO) ₄ ( μ-CO)(μ-PPh ₂ ) . / Hashimoto, Hisako ; Tobita, Hiromi; Ogino, Hiroshi.

In: Journal of Organometallic Chemistry, Vol. 499, No. 1-2, 06.09.1995, p. 205-211.

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

Hashimoto, H , Tobita, H & Ogino, H 1995, ' Redistribution reactions of hydrosilanes mediated by the unsymmetrical and homometallic phosphido-bridged complex (η ⁵ -C ₅ Me ₅ )Fe ₂ (CO) ₄ ( μ-CO)(μ-PPh ₂ ) ', Journal of Organometallic Chemistry, vol. 499, no. 1-2, pp. 205-211. https://doi.org/10.1016/0022-328X(95)00301-6

Hashimoto H , Tobita H, Ogino H. Redistribution reactions of hydrosilanes mediated by the unsymmetrical and homometallic phosphido-bridged complex (η ⁵ -C ₅ Me ₅ )Fe ₂ (CO) ₄ ( μ-CO)(μ-PPh ₂ ) Journal of Organometallic Chemistry. 1995 Sept 6;499(1-2):205-211. doi: 10.1016/0022-328X(95)00301-6

Hashimoto, Hisako ; Tobita, Hiromi ; Ogino, Hiroshi. / Redistribution reactions of hydrosilanes mediated by the unsymmetrical and homometallic phosphido-bridged complex (η ⁵ -C ₅ Me ₅ )Fe ₂ (CO) ₄ ( μ-CO)(μ-PPh ₂ ) In: Journal of Organometallic Chemistry. 1995 ; Vol. 499, No. 1-2. pp. 205-211.

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title = " Redistribution reactions of hydrosilanes mediated by the unsymmetrical and homometallic phosphido-bridged complex (η 5 -C 5 Me 5 )Fe 2 (CO) 4 ( μ-CO)(μ-PPh 2 ) ",

abstract = " Reactions of the unsymmetrical and homobimetallic phosphido-bridged complex (η 5 -C 5 Me 5 )Fe 2 (CO) 4 (μ-CO)(μ-PPh 2 ) (1) with various hydrosilanes gave rise to redistribution of the substituents on hydrosilanes. The reaction of 1 with 2 equiv. of secondary silane R 2 SiH 2 (R = Ph, p-Tol) caused effective aryl scrambling to afford a monoarylsilylene-bridged complex (η 5 -C 5 Me 5 )Fe 2 (CO) 4 (μ-SiRH)(μ-PPh 2 ) (2, R = Ph; 3, R = p-Tol) and a tertiary silane R 3 SiH (R = Ph, p-Tol). The signals of 29 Si and 31 P 1 H NMR spectra of these complexes appear at very low field ( 29 Si NMR; 2, δ 209.1, 1 J(SiH) = 185 Hz, 2 J(SiP) = 26 Hz; 3, δ 209.1 1 J(SiH) = 185 Hz, 2 J(SiP) = 27 Hz. 31 P NMR: 2, δ 224.5: 3, δ 225.0). Complex 2 and Ph 3 SiH were also formed by the reaction of 1 with 1 equiv. of dihydrodisilane HPh 2 SiSiPh 2 H. Similarly, the reaction of 1 with alkyldisilane HMe 2 SiSiMe 2 H proceeded smoothly to give the alkyl-scrambling product (η 5 -C 5 Me 5 )Fe 2 (CO) 4 (μ-SiMeH)(μ-PPh 2 ) (4) and Me 3 SiH. Some intermediates were observed in each reaction by NMR spectroscopy. A reaction mechanism containing silyl(silylene) intermediates is proposed.",

keywords = "Carbonyl, Cyclopentadienyl, Iron, Phosphorus, Silane, Silylene",

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AU - Hashimoto, Hisako

AU - Tobita, Hiromi

AU - Ogino, Hiroshi

PY - 1995/9/6

Y1 - 1995/9/6

N2 - Reactions of the unsymmetrical and homobimetallic phosphido-bridged complex (η 5 -C 5 Me 5 )Fe 2 (CO) 4 (μ-CO)(μ-PPh 2 ) (1) with various hydrosilanes gave rise to redistribution of the substituents on hydrosilanes. The reaction of 1 with 2 equiv. of secondary silane R 2 SiH 2 (R = Ph, p-Tol) caused effective aryl scrambling to afford a monoarylsilylene-bridged complex (η 5 -C 5 Me 5 )Fe 2 (CO) 4 (μ-SiRH)(μ-PPh 2 ) (2, R = Ph; 3, R = p-Tol) and a tertiary silane R 3 SiH (R = Ph, p-Tol). The signals of 29 Si and 31 P 1 H NMR spectra of these complexes appear at very low field ( 29 Si NMR; 2, δ 209.1, 1 J(SiH) = 185 Hz, 2 J(SiP) = 26 Hz; 3, δ 209.1 1 J(SiH) = 185 Hz, 2 J(SiP) = 27 Hz. 31 P NMR: 2, δ 224.5: 3, δ 225.0). Complex 2 and Ph 3 SiH were also formed by the reaction of 1 with 1 equiv. of dihydrodisilane HPh 2 SiSiPh 2 H. Similarly, the reaction of 1 with alkyldisilane HMe 2 SiSiMe 2 H proceeded smoothly to give the alkyl-scrambling product (η 5 -C 5 Me 5 )Fe 2 (CO) 4 (μ-SiMeH)(μ-PPh 2 ) (4) and Me 3 SiH. Some intermediates were observed in each reaction by NMR spectroscopy. A reaction mechanism containing silyl(silylene) intermediates is proposed.

AB - Reactions of the unsymmetrical and homobimetallic phosphido-bridged complex (η 5 -C 5 Me 5 )Fe 2 (CO) 4 (μ-CO)(μ-PPh 2 ) (1) with various hydrosilanes gave rise to redistribution of the substituents on hydrosilanes. The reaction of 1 with 2 equiv. of secondary silane R 2 SiH 2 (R = Ph, p-Tol) caused effective aryl scrambling to afford a monoarylsilylene-bridged complex (η 5 -C 5 Me 5 )Fe 2 (CO) 4 (μ-SiRH)(μ-PPh 2 ) (2, R = Ph; 3, R = p-Tol) and a tertiary silane R 3 SiH (R = Ph, p-Tol). The signals of 29 Si and 31 P 1 H NMR spectra of these complexes appear at very low field ( 29 Si NMR; 2, δ 209.1, 1 J(SiH) = 185 Hz, 2 J(SiP) = 26 Hz; 3, δ 209.1 1 J(SiH) = 185 Hz, 2 J(SiP) = 27 Hz. 31 P NMR: 2, δ 224.5: 3, δ 225.0). Complex 2 and Ph 3 SiH were also formed by the reaction of 1 with 1 equiv. of dihydrodisilane HPh 2 SiSiPh 2 H. Similarly, the reaction of 1 with alkyldisilane HMe 2 SiSiMe 2 H proceeded smoothly to give the alkyl-scrambling product (η 5 -C 5 Me 5 )Fe 2 (CO) 4 (μ-SiMeH)(μ-PPh 2 ) (4) and Me 3 SiH. Some intermediates were observed in each reaction by NMR spectroscopy. A reaction mechanism containing silyl(silylene) intermediates is proposed.

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KW - Phosphorus

KW - Silane

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