Multi-insertion reactions of isocyanides with zirconium amido silyl complexes

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Abstract

The reactions of (Me2N)3ZrSi(SiMe3)3 (1), (Me2N)3ZrSiPh2But(THF)o.5 (2), and (Me2N)2[(Me3Si)2N]ZrSi(SiMe 3)3 (3) with 2,6-dimethylphenyl isocyanide (ArNC) or tert-butyl isocyanide (ButNC) have been investigated. The first ArNC was found to insert exclusively into the Zi-Si bond in complex 3 and, in contrast, into the Zi-N bonds in complex 1. Up to 4 equiv of ArNC react with 1 and 2 to give (Me2N)2Zr[Si(SiMe3)3][η 3-C(NMe2)=NAr] (4), (Me2N)Zr[Si(SiMe3)3][η3-C(NMe 2)=NAr]2 (5), (Me2N)Zr[η2-C(NMe2)=NAr] 22-C[Si(SiMe3)3]=NAr} (6), Zr[η2-C(NMe2)=NAr]33-C[Si(SiMe3)3]=NAr} (7), and Zr[η2-C(NMe2)=NAr]32-C(SiPh2But) =NAr] (8). However, 3 reacts with only 2 equiv of ArNC to yield (Me2N)2[(Me3Si)2N]Zr{η 2-C[Si(SiMe3)3]=NAr} (9) and (Me2N)[(Me3Si)2N]Zr[η 2-C(NMe2)=NAr]{η2-C[Si(SiMe3)3]=NAr} (10). Complex 2 was found to react with 2 equiv of ButNC to yield a ketenimine complex (Me2N)3Zr[N(But)C(SiPh2But)=C=NBut] (12). The reactions of Zr(NMe2)4 with ArNC and Bu'NC were also studied and gave tetrainsertion products Zr[η2-C(NMe2)=NR]4 [R = Bu*(13), 2,6-dimethylphenyl (14)]. The structures of 7,12,13, and 14 have been determined by X-ray crystallography.

Original languageEnglish (US)
Pages (from-to)1002-1010
Number of pages9
JournalOrganometallics
Volume18
Issue number6
DOIs
StatePublished - Mar 15 1999

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X ray crystallography
Cyanides
insertion
inserts
crystallography
products
x rays
ketenimine
tert-butyl isocyanide
2,6-dimethylphenyl isocyanide

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Multi-insertion reactions of isocyanides with zirconium amido silyl complexes. / Wu, Zhongzhi.

In: Organometallics, Vol. 18, No. 6, 15.03.1999, p. 1002-1010.

Research output: Contribution to journalArticle

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title = "Multi-insertion reactions of isocyanides with zirconium amido silyl complexes",
abstract = "The reactions of (Me2N)3ZrSi(SiMe3)3 (1), (Me2N)3ZrSiPh2But(THF)o.5 (2), and (Me2N)2[(Me3Si)2N]ZrSi(SiMe 3)3 (3) with 2,6-dimethylphenyl isocyanide (ArNC) or tert-butyl isocyanide (ButNC) have been investigated. The first ArNC was found to insert exclusively into the Zi-Si bond in complex 3 and, in contrast, into the Zi-N bonds in complex 1. Up to 4 equiv of ArNC react with 1 and 2 to give (Me2N)2Zr[Si(SiMe3)3][η 3-C(NMe2)=NAr] (4), (Me2N)Zr[Si(SiMe3)3][η3-C(NMe 2)=NAr]2 (5), (Me2N)Zr[η2-C(NMe2)=NAr] 2{η2-C[Si(SiMe3)3]=NAr} (6), Zr[η2-C(NMe2)=NAr]3{η 3-C[Si(SiMe3)3]=NAr} (7), and Zr[η2-C(NMe2)=NAr]3[η 2-C(SiPh2But) =NAr] (8). However, 3 reacts with only 2 equiv of ArNC to yield (Me2N)2[(Me3Si)2N]Zr{η 2-C[Si(SiMe3)3]=NAr} (9) and (Me2N)[(Me3Si)2N]Zr[η 2-C(NMe2)=NAr]{η2-C[Si(SiMe3)3]=NAr} (10). Complex 2 was found to react with 2 equiv of ButNC to yield a ketenimine complex (Me2N)3Zr[N(But)C(SiPh2But)=C=NBut] (12). The reactions of Zr(NMe2)4 with ArNC and Bu'NC were also studied and gave tetrainsertion products Zr[η2-C(NMe2)=NR]4 [R = Bu*(13), 2,6-dimethylphenyl (14)]. The structures of 7,12,13, and 14 have been determined by X-ray crystallography.",
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N2 - The reactions of (Me2N)3ZrSi(SiMe3)3 (1), (Me2N)3ZrSiPh2But(THF)o.5 (2), and (Me2N)2[(Me3Si)2N]ZrSi(SiMe 3)3 (3) with 2,6-dimethylphenyl isocyanide (ArNC) or tert-butyl isocyanide (ButNC) have been investigated. The first ArNC was found to insert exclusively into the Zi-Si bond in complex 3 and, in contrast, into the Zi-N bonds in complex 1. Up to 4 equiv of ArNC react with 1 and 2 to give (Me2N)2Zr[Si(SiMe3)3][η 3-C(NMe2)=NAr] (4), (Me2N)Zr[Si(SiMe3)3][η3-C(NMe 2)=NAr]2 (5), (Me2N)Zr[η2-C(NMe2)=NAr] 2{η2-C[Si(SiMe3)3]=NAr} (6), Zr[η2-C(NMe2)=NAr]3{η 3-C[Si(SiMe3)3]=NAr} (7), and Zr[η2-C(NMe2)=NAr]3[η 2-C(SiPh2But) =NAr] (8). However, 3 reacts with only 2 equiv of ArNC to yield (Me2N)2[(Me3Si)2N]Zr{η 2-C[Si(SiMe3)3]=NAr} (9) and (Me2N)[(Me3Si)2N]Zr[η 2-C(NMe2)=NAr]{η2-C[Si(SiMe3)3]=NAr} (10). Complex 2 was found to react with 2 equiv of ButNC to yield a ketenimine complex (Me2N)3Zr[N(But)C(SiPh2But)=C=NBut] (12). The reactions of Zr(NMe2)4 with ArNC and Bu'NC were also studied and gave tetrainsertion products Zr[η2-C(NMe2)=NR]4 [R = Bu*(13), 2,6-dimethylphenyl (14)]. The structures of 7,12,13, and 14 have been determined by X-ray crystallography.

AB - The reactions of (Me2N)3ZrSi(SiMe3)3 (1), (Me2N)3ZrSiPh2But(THF)o.5 (2), and (Me2N)2[(Me3Si)2N]ZrSi(SiMe 3)3 (3) with 2,6-dimethylphenyl isocyanide (ArNC) or tert-butyl isocyanide (ButNC) have been investigated. The first ArNC was found to insert exclusively into the Zi-Si bond in complex 3 and, in contrast, into the Zi-N bonds in complex 1. Up to 4 equiv of ArNC react with 1 and 2 to give (Me2N)2Zr[Si(SiMe3)3][η 3-C(NMe2)=NAr] (4), (Me2N)Zr[Si(SiMe3)3][η3-C(NMe 2)=NAr]2 (5), (Me2N)Zr[η2-C(NMe2)=NAr] 2{η2-C[Si(SiMe3)3]=NAr} (6), Zr[η2-C(NMe2)=NAr]3{η 3-C[Si(SiMe3)3]=NAr} (7), and Zr[η2-C(NMe2)=NAr]3[η 2-C(SiPh2But) =NAr] (8). However, 3 reacts with only 2 equiv of ArNC to yield (Me2N)2[(Me3Si)2N]Zr{η 2-C[Si(SiMe3)3]=NAr} (9) and (Me2N)[(Me3Si)2N]Zr[η 2-C(NMe2)=NAr]{η2-C[Si(SiMe3)3]=NAr} (10). Complex 2 was found to react with 2 equiv of ButNC to yield a ketenimine complex (Me2N)3Zr[N(But)C(SiPh2But)=C=NBut] (12). The reactions of Zr(NMe2)4 with ArNC and Bu'NC were also studied and gave tetrainsertion products Zr[η2-C(NMe2)=NR]4 [R = Bu*(13), 2,6-dimethylphenyl (14)]. The structures of 7,12,13, and 14 have been determined by X-ray crystallography.

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