Reactions of (Me3ECH2)3ZrSi(SiMe3)3 (E = C, Si) with 2,6-dimethylphenyl isocyanide. Preferential isocyanide insertion into Zr-silyl bonds

Zhongzhi Wu, Lenore H. McAlexander, Jonathan B. Diminnie, Ziling Xue

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Abstract

The reactions of alkyl silyl complexes (Me3ECH2)3ZrSi(SiMe3)3 [E = C (1), Si (2)] with 2,6-dimethylphenyl isocyanide (ArNC) have been investigated. The first ArNC was found to insert exclusively into the Zr-Si bond, and the second and third ArNC into the Zr-C bonds in 1 and 2. 1 and 2 react with up to 3 equiv of ArNC to give (Me3ECH2)3Zr{η2-C[Si-(SiMe 3)3]=NAr} [E = C (3), Si (4)], (Me3ECH2)2Zr[η2-C(CH 2EMe3)=NAr]{η2-C[Si(SiMe3) 3]=NAr} [E = C (5), Si (6)], and (Me3ECH2Zr[η2-C(CH2EMe 3)=NAr]22-C[Si(SiMe3) 3]=NAr} [E = C (7), Si (8)]. The tri-insertion complexes 7 and 8 are inert to excess ArNC. The structures of 3 and 7 have been determined by X-ray crystallography. In the structure of 3, the α-hydrogen atoms on one neopentyl ligand lie in close contact (av 2.41 Å) with the metal center giving rise to Zr-C-Hα bond angles of 90 and 92°. The crystal structure of the precursor 1 has also been determined.

Original languageEnglish (US)
Pages (from-to)4853-4860
Number of pages8
JournalOrganometallics
Volume17
Issue number22
StatePublished - Oct 26 1998

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X ray crystallography
Cyanides
inserts
crystallography
insertion
Hydrogen
hydrogen atoms
Crystal structure
Metals
methylidyne
Ligands
Atoms
ligands
crystal structure
metals
x rays
2,6-dimethylphenyl isocyanide

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Reactions of (Me3ECH2)3ZrSi(SiMe3)3 (E = C, Si) with 2,6-dimethylphenyl isocyanide. Preferential isocyanide insertion into Zr-silyl bonds. / Wu, Zhongzhi; McAlexander, Lenore H.; Diminnie, Jonathan B.; Xue, Ziling.

In: Organometallics, Vol. 17, No. 22, 26.10.1998, p. 4853-4860.

Research output: Contribution to journalArticle

Wu, Zhongzhi ; McAlexander, Lenore H. ; Diminnie, Jonathan B. ; Xue, Ziling. / Reactions of (Me3ECH2)3ZrSi(SiMe3)3 (E = C, Si) with 2,6-dimethylphenyl isocyanide. Preferential isocyanide insertion into Zr-silyl bonds. In: Organometallics. 1998 ; Vol. 17, No. 22. pp. 4853-4860.
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abstract = "The reactions of alkyl silyl complexes (Me3ECH2)3ZrSi(SiMe3)3 [E = C (1), Si (2)] with 2,6-dimethylphenyl isocyanide (ArNC) have been investigated. The first ArNC was found to insert exclusively into the Zr-Si bond, and the second and third ArNC into the Zr-C bonds in 1 and 2. 1 and 2 react with up to 3 equiv of ArNC to give (Me3ECH2)3Zr{η2-C[Si-(SiMe 3)3]=NAr} [E = C (3), Si (4)], (Me3ECH2)2Zr[η2-C(CH 2EMe3)=NAr]{η2-C[Si(SiMe3) 3]=NAr} [E = C (5), Si (6)], and (Me3ECH2Zr[η2-C(CH2EMe 3)=NAr]2{η2-C[Si(SiMe3) 3]=NAr} [E = C (7), Si (8)]. The tri-insertion complexes 7 and 8 are inert to excess ArNC. The structures of 3 and 7 have been determined by X-ray crystallography. In the structure of 3, the α-hydrogen atoms on one neopentyl ligand lie in close contact (av 2.41 {\AA}) with the metal center giving rise to Zr-C-Hα bond angles of 90 and 92°. The crystal structure of the precursor 1 has also been determined.",
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N2 - The reactions of alkyl silyl complexes (Me3ECH2)3ZrSi(SiMe3)3 [E = C (1), Si (2)] with 2,6-dimethylphenyl isocyanide (ArNC) have been investigated. The first ArNC was found to insert exclusively into the Zr-Si bond, and the second and third ArNC into the Zr-C bonds in 1 and 2. 1 and 2 react with up to 3 equiv of ArNC to give (Me3ECH2)3Zr{η2-C[Si-(SiMe 3)3]=NAr} [E = C (3), Si (4)], (Me3ECH2)2Zr[η2-C(CH 2EMe3)=NAr]{η2-C[Si(SiMe3) 3]=NAr} [E = C (5), Si (6)], and (Me3ECH2Zr[η2-C(CH2EMe 3)=NAr]2{η2-C[Si(SiMe3) 3]=NAr} [E = C (7), Si (8)]. The tri-insertion complexes 7 and 8 are inert to excess ArNC. The structures of 3 and 7 have been determined by X-ray crystallography. In the structure of 3, the α-hydrogen atoms on one neopentyl ligand lie in close contact (av 2.41 Å) with the metal center giving rise to Zr-C-Hα bond angles of 90 and 92°. The crystal structure of the precursor 1 has also been determined.

AB - The reactions of alkyl silyl complexes (Me3ECH2)3ZrSi(SiMe3)3 [E = C (1), Si (2)] with 2,6-dimethylphenyl isocyanide (ArNC) have been investigated. The first ArNC was found to insert exclusively into the Zr-Si bond, and the second and third ArNC into the Zr-C bonds in 1 and 2. 1 and 2 react with up to 3 equiv of ArNC to give (Me3ECH2)3Zr{η2-C[Si-(SiMe 3)3]=NAr} [E = C (3), Si (4)], (Me3ECH2)2Zr[η2-C(CH 2EMe3)=NAr]{η2-C[Si(SiMe3) 3]=NAr} [E = C (5), Si (6)], and (Me3ECH2Zr[η2-C(CH2EMe 3)=NAr]2{η2-C[Si(SiMe3) 3]=NAr} [E = C (7), Si (8)]. The tri-insertion complexes 7 and 8 are inert to excess ArNC. The structures of 3 and 7 have been determined by X-ray crystallography. In the structure of 3, the α-hydrogen atoms on one neopentyl ligand lie in close contact (av 2.41 Å) with the metal center giving rise to Zr-C-Hα bond angles of 90 and 92°. The crystal structure of the precursor 1 has also been determined.

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