Synthesis and characterization of dmap-stabilized aryl(silylene) complexes and (arylsilyl)(dmap) complexes of tungsten mechanistic study on the interconversion between these complexes via 1,2-aryl migration

Eiji Suzuki; Takashi Komuro; Masaaki Okazaki; Hiromi Tobita

doi:10.1021/om801140d

Synthesis and characterization of dmap-stabilized aryl(silylene) complexes and (arylsilyl)(dmap) complexes of tungsten mechanistic study on the interconversion between these complexes via 1,2-aryl migration

Eiji Suzuki, Takashi Komuro, Masaaki Okazaki, Hiromi Tobita

SCI - Chemistry

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

19 Citations (Scopus)

Abstract

Photoreaction of a mixture of Cp*(CO)₃WMe (Cp* = η⁵-C₅Me₅) and HSiR₂Ar [R ₂Ar = Me₂Ph, Me₂(p-Tol), Me(p-Tol)₂, and (p-Tol)₂] in the presence of 4-(dimethylamino)pyridine (DMAP) gave DMAP-stabilized aryl(silylene) complexes Cp*(CO)₂W(Ar)(= SiR2-DMAP) [la, R = Me, Ar = Ph; lb, R = Me, Ar = p-Tol; lc, R₂ = Me(p-Tol), Ar = p-Tol; Id, R = Ar = p-Tol] via 1,2-migration of the aryl group from a silyl ligand to a tungsten center. Thermal reactions of Cp*(CO)₂W(DMAP)Me (2) with HSiR₂Ar at room temperature also gave la - d, and in all cases the yields were higher than those in the photoreaction. Silylene complexes la - d easily isomerized to arylsilyl complexes Cp*(CO)₂- W(DMAP)(SiR₂Ar) [3a, R = Me, Ar = Ph; 3b, R = Me, Ar = p-Tol; 3c, R, = Me(p-Tol), Ar = p-Tol; 3d, R = Ar = p-Tol] at 40-55 °C. On the other hand, irradiation of arylsilyl complexes 3a - d reproduced silylene complexes la - d, implying that the 1,2-aryl-migration between tungsten and silicon is reversible. The molecular structures of lc, 2, 3a, and 3d were determined by X-ray crystallography. A kinetic study on the 1,2-aryl-migration in the thermal isomerization from la - d to 3a - d suggests that the rate-determining step involves dissociation of DMAP from la - d.

Original language	English
Pages (from-to)	1791-1799
Number of pages	9
Journal	Organometallics
Volume	28
Issue number	6
DOIs	https://doi.org/10.1021/om801140d
Publication status	Published - 2009 Mar 23

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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Synthesis and characterization of dmap-stabilized aryl(silylene) complexes and (arylsilyl)(dmap) complexes of tungsten mechanistic study on the interconversion between these complexes via 1,2-aryl migration. / Suzuki, Eiji; Komuro, Takashi; Okazaki, Masaaki; Tobita, Hiromi.

In: Organometallics, Vol. 28, No. 6, 23.03.2009, p. 1791-1799.

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

@article{2685cf7a81fa47ff8819f11cf60d2f46,

title = "Synthesis and characterization of dmap-stabilized aryl(silylene) complexes and (arylsilyl)(dmap) complexes of tungsten mechanistic study on the interconversion between these complexes via 1,2-aryl migration",

abstract = "Photoreaction of a mixture of Cp*(CO)3WMe (Cp* = η5-C5Me5) and HSiR2Ar [R 2Ar = Me2Ph, Me2(p-Tol), Me(p-Tol)2, and (p-Tol)2] in the presence of 4-(dimethylamino)pyridine (DMAP) gave DMAP-stabilized aryl(silylene) complexes Cp*(CO)2W(Ar)(= SiR2-DMAP) [la, R = Me, Ar = Ph; lb, R = Me, Ar = p-Tol; lc, R2 = Me(p-Tol), Ar = p-Tol; Id, R = Ar = p-Tol] via 1,2-migration of the aryl group from a silyl ligand to a tungsten center. Thermal reactions of Cp*(CO)2W(DMAP)Me (2) with HSiR2Ar at room temperature also gave la - d, and in all cases the yields were higher than those in the photoreaction. Silylene complexes la - d easily isomerized to arylsilyl complexes Cp*(CO)2- W(DMAP)(SiR2Ar) [3a, R = Me, Ar = Ph; 3b, R = Me, Ar = p-Tol; 3c, R, = Me(p-Tol), Ar = p-Tol; 3d, R = Ar = p-Tol] at 40-55 °C. On the other hand, irradiation of arylsilyl complexes 3a - d reproduced silylene complexes la - d, implying that the 1,2-aryl-migration between tungsten and silicon is reversible. The molecular structures of lc, 2, 3a, and 3d were determined by X-ray crystallography. A kinetic study on the 1,2-aryl-migration in the thermal isomerization from la - d to 3a - d suggests that the rate-determining step involves dissociation of DMAP from la - d.",

author = "Eiji Suzuki and Takashi Komuro and Masaaki Okazaki and Hiromi Tobita",

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T1 - Synthesis and characterization of dmap-stabilized aryl(silylene) complexes and (arylsilyl)(dmap) complexes of tungsten mechanistic study on the interconversion between these complexes via 1,2-aryl migration

AU - Suzuki, Eiji

AU - Komuro, Takashi

AU - Okazaki, Masaaki

AU - Tobita, Hiromi

PY - 2009/3/23

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N2 - Photoreaction of a mixture of Cp*(CO)3WMe (Cp* = η5-C5Me5) and HSiR2Ar [R 2Ar = Me2Ph, Me2(p-Tol), Me(p-Tol)2, and (p-Tol)2] in the presence of 4-(dimethylamino)pyridine (DMAP) gave DMAP-stabilized aryl(silylene) complexes Cp*(CO)2W(Ar)(= SiR2-DMAP) [la, R = Me, Ar = Ph; lb, R = Me, Ar = p-Tol; lc, R2 = Me(p-Tol), Ar = p-Tol; Id, R = Ar = p-Tol] via 1,2-migration of the aryl group from a silyl ligand to a tungsten center. Thermal reactions of Cp*(CO)2W(DMAP)Me (2) with HSiR2Ar at room temperature also gave la - d, and in all cases the yields were higher than those in the photoreaction. Silylene complexes la - d easily isomerized to arylsilyl complexes Cp*(CO)2- W(DMAP)(SiR2Ar) [3a, R = Me, Ar = Ph; 3b, R = Me, Ar = p-Tol; 3c, R, = Me(p-Tol), Ar = p-Tol; 3d, R = Ar = p-Tol] at 40-55 °C. On the other hand, irradiation of arylsilyl complexes 3a - d reproduced silylene complexes la - d, implying that the 1,2-aryl-migration between tungsten and silicon is reversible. The molecular structures of lc, 2, 3a, and 3d were determined by X-ray crystallography. A kinetic study on the 1,2-aryl-migration in the thermal isomerization from la - d to 3a - d suggests that the rate-determining step involves dissociation of DMAP from la - d.

AB - Photoreaction of a mixture of Cp*(CO)3WMe (Cp* = η5-C5Me5) and HSiR2Ar [R 2Ar = Me2Ph, Me2(p-Tol), Me(p-Tol)2, and (p-Tol)2] in the presence of 4-(dimethylamino)pyridine (DMAP) gave DMAP-stabilized aryl(silylene) complexes Cp*(CO)2W(Ar)(= SiR2-DMAP) [la, R = Me, Ar = Ph; lb, R = Me, Ar = p-Tol; lc, R2 = Me(p-Tol), Ar = p-Tol; Id, R = Ar = p-Tol] via 1,2-migration of the aryl group from a silyl ligand to a tungsten center. Thermal reactions of Cp*(CO)2W(DMAP)Me (2) with HSiR2Ar at room temperature also gave la - d, and in all cases the yields were higher than those in the photoreaction. Silylene complexes la - d easily isomerized to arylsilyl complexes Cp*(CO)2- W(DMAP)(SiR2Ar) [3a, R = Me, Ar = Ph; 3b, R = Me, Ar = p-Tol; 3c, R, = Me(p-Tol), Ar = p-Tol; 3d, R = Ar = p-Tol] at 40-55 °C. On the other hand, irradiation of arylsilyl complexes 3a - d reproduced silylene complexes la - d, implying that the 1,2-aryl-migration between tungsten and silicon is reversible. The molecular structures of lc, 2, 3a, and 3d were determined by X-ray crystallography. A kinetic study on the 1,2-aryl-migration in the thermal isomerization from la - d to 3a - d suggests that the rate-determining step involves dissociation of DMAP from la - d.

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