Synthesis, structure, and bonding of stable dialkylsilaketenimines

Takashi Abe; Takeaki Iwamoto; Chizuko Kabuto; Mitsuo Kira

doi:10.1021/ja057917o

Synthesis, structure, and bonding of stable dialkylsilaketenimines

Takashi Abe, Takeaki Iwamoto, Chizuko Kabuto, Mitsuo Kira

SCI - Chemistry

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

58 Citations (Scopus)

Abstract

Stable (N-aryl)- and (N-alkyl)dialkylsilaketenimines R₂SiCNR′ [R = 1,1,4,4-tetrakis(trimethylsilyl)butane-1,4-diyl, R′ = 2,6-diisopropylphenyl (2a) and 1-adamantyl (2b)] were synthesized as blue and red crystals by the reactions of isolable dialkylsilylene 3 with 2,6-diisopropylphenyl isocyanide and 1-adamantyl isocyanide. X-ray single-crystal analysis disclosed that molecular structures of 2a and 2b were close to each other and were characterized to be allenic rather than zwitterionic or a silylene-isocyanide complex. The bonding characteristics of silaketenimines are found to be affected strongly by the substituents on silicon and nitrogen atoms. Remarkable red-shift of the π(Si=C) → π*(C=N) band of 2a [λ_max/nm (ε) 647(156)] compared with that of 2b [465 nm (109)] is ascribed to lowering of the π*(C=N) orbital level due to significant interaction between π*(C=N) and π*(N-aryl) orbitals.

Original language	English
Pages (from-to)	4228-4229
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	128
Issue number	13
DOIs	https://doi.org/10.1021/ja057917o
Publication status	Published - 2006 Apr 5

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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title = "Synthesis, structure, and bonding of stable dialkylsilaketenimines",

abstract = "Stable (N-aryl)- and (N-alkyl)dialkylsilaketenimines R2SiCNR′ [R = 1,1,4,4-tetrakis(trimethylsilyl)butane-1,4-diyl, R′ = 2,6-diisopropylphenyl (2a) and 1-adamantyl (2b)] were synthesized as blue and red crystals by the reactions of isolable dialkylsilylene 3 with 2,6-diisopropylphenyl isocyanide and 1-adamantyl isocyanide. X-ray single-crystal analysis disclosed that molecular structures of 2a and 2b were close to each other and were characterized to be allenic rather than zwitterionic or a silylene-isocyanide complex. The bonding characteristics of silaketenimines are found to be affected strongly by the substituents on silicon and nitrogen atoms. Remarkable red-shift of the π(Si=C) → π*(C=N) band of 2a [λmax/nm (ε) 647(156)] compared with that of 2b [465 nm (109)] is ascribed to lowering of the π*(C=N) orbital level due to significant interaction between π*(C=N) and π*(N-aryl) orbitals.",

author = "Takashi Abe and Takeaki Iwamoto and Chizuko Kabuto and Mitsuo Kira",

year = "2006",

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AU - Abe, Takashi

AU - Iwamoto, Takeaki

AU - Kabuto, Chizuko

AU - Kira, Mitsuo

PY - 2006/4/5

Y1 - 2006/4/5

N2 - Stable (N-aryl)- and (N-alkyl)dialkylsilaketenimines R2SiCNR′ [R = 1,1,4,4-tetrakis(trimethylsilyl)butane-1,4-diyl, R′ = 2,6-diisopropylphenyl (2a) and 1-adamantyl (2b)] were synthesized as blue and red crystals by the reactions of isolable dialkylsilylene 3 with 2,6-diisopropylphenyl isocyanide and 1-adamantyl isocyanide. X-ray single-crystal analysis disclosed that molecular structures of 2a and 2b were close to each other and were characterized to be allenic rather than zwitterionic or a silylene-isocyanide complex. The bonding characteristics of silaketenimines are found to be affected strongly by the substituents on silicon and nitrogen atoms. Remarkable red-shift of the π(Si=C) → π*(C=N) band of 2a [λmax/nm (ε) 647(156)] compared with that of 2b [465 nm (109)] is ascribed to lowering of the π*(C=N) orbital level due to significant interaction between π*(C=N) and π*(N-aryl) orbitals.

AB - Stable (N-aryl)- and (N-alkyl)dialkylsilaketenimines R2SiCNR′ [R = 1,1,4,4-tetrakis(trimethylsilyl)butane-1,4-diyl, R′ = 2,6-diisopropylphenyl (2a) and 1-adamantyl (2b)] were synthesized as blue and red crystals by the reactions of isolable dialkylsilylene 3 with 2,6-diisopropylphenyl isocyanide and 1-adamantyl isocyanide. X-ray single-crystal analysis disclosed that molecular structures of 2a and 2b were close to each other and were characterized to be allenic rather than zwitterionic or a silylene-isocyanide complex. The bonding characteristics of silaketenimines are found to be affected strongly by the substituents on silicon and nitrogen atoms. Remarkable red-shift of the π(Si=C) → π*(C=N) band of 2a [λmax/nm (ε) 647(156)] compared with that of 2b [465 nm (109)] is ascribed to lowering of the π*(C=N) orbital level due to significant interaction between π*(C=N) and π*(N-aryl) orbitals.

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Synthesis, structure, and bonding of stable dialkylsilaketenimines

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