Insertion reactions of phenyl isocyanate into hafnium nitrogen bonds: Synthesis and reactivity of hafnium complexes bearing substituted pyrrolyl ligands

Kun Chun Hsieh, Wen Yi Lee, Chun Liang Lai, Ching Han Hu, Hon Man Lee, Jui Hsien Huang, Shie Ming Peng, Gene Hsing Lee

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

A bis(diethylamido)hafnium compound [C4(CH2NMe 2)-2]2Hf(NEt2)2 (1) has been prepared in 79% yield by reacting Hf(NEt2)4 with 2 equiv. of [C4H(CH2NMe2)-2] in heptane via deamination. Reacting compound 1 with 2 equiv. of phenyl isocyanate at room temperature in diethyl ether results in the PhNCO being inserted seletively into hafnium-NEt2 bonds to generate [C4(CH2NMe2)-2]2Hf[PhNC (NEt2)O]2 (2) in 56% yield. Similarly, while reacting 1 with 2 equiv. of phenyl isocyanate for a week in toluene produces a mixture of 2 and [C4(CH2NMe 2)-2]Hf[PhNC(NEt2)O]3 (3). For comparison, reacting Hf(NEt2)4 with 4 equiv. of PhNCO in a toluene solution at room temperature results in the PhNCO inserted into Hf-N bonds, and forms a tetrakis-ureato hafnium compound Hf[PhNC(NEt2)O]4 (4) in 88% yield. A theoretical calculation found that the unpaired electrons of the ureato fragments of 2 are resonance delocalized between the C-O, C-NPh, and C-NEt2 bonds, which are all partially doubly bonded.

Original languageEnglish (US)
Pages (from-to)3362-3369
Number of pages8
JournalJournal of Organometallic Chemistry
Volume689
Issue number21
DOIs
StatePublished - Oct 15 2004
Externally publishedYes

Fingerprint

Hafnium compounds
Bearings (structural)
Hafnium
isocyanates
hafnium compounds
hafnium
Toluene
insertion
Nitrogen
reactivity
Ligands
Heptanes
nitrogen
ligands
toluene
Heptane
synthesis
Ether
Ethers
Deamination

Keywords

  • Insertion hafnium
  • Phenyl isocyanate
  • Pyrrolyl

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Insertion reactions of phenyl isocyanate into hafnium nitrogen bonds : Synthesis and reactivity of hafnium complexes bearing substituted pyrrolyl ligands. / Hsieh, Kun Chun; Lee, Wen Yi; Lai, Chun Liang; Hu, Ching Han; Lee, Hon Man; Huang, Jui Hsien; Peng, Shie Ming; Lee, Gene Hsing.

In: Journal of Organometallic Chemistry, Vol. 689, No. 21, 15.10.2004, p. 3362-3369.

Research output: Contribution to journalArticle

Hsieh, Kun Chun ; Lee, Wen Yi ; Lai, Chun Liang ; Hu, Ching Han ; Lee, Hon Man ; Huang, Jui Hsien ; Peng, Shie Ming ; Lee, Gene Hsing. / Insertion reactions of phenyl isocyanate into hafnium nitrogen bonds : Synthesis and reactivity of hafnium complexes bearing substituted pyrrolyl ligands. In: Journal of Organometallic Chemistry. 2004 ; Vol. 689, No. 21. pp. 3362-3369.
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abstract = "A bis(diethylamido)hafnium compound [C4(CH2NMe 2)-2]2Hf(NEt2)2 (1) has been prepared in 79{\%} yield by reacting Hf(NEt2)4 with 2 equiv. of [C4H(CH2NMe2)-2] in heptane via deamination. Reacting compound 1 with 2 equiv. of phenyl isocyanate at room temperature in diethyl ether results in the PhNCO being inserted seletively into hafnium-NEt2 bonds to generate [C4(CH2NMe2)-2]2Hf[PhNC (NEt2)O]2 (2) in 56{\%} yield. Similarly, while reacting 1 with 2 equiv. of phenyl isocyanate for a week in toluene produces a mixture of 2 and [C4(CH2NMe 2)-2]Hf[PhNC(NEt2)O]3 (3). For comparison, reacting Hf(NEt2)4 with 4 equiv. of PhNCO in a toluene solution at room temperature results in the PhNCO inserted into Hf-N bonds, and forms a tetrakis-ureato hafnium compound Hf[PhNC(NEt2)O]4 (4) in 88{\%} yield. A theoretical calculation found that the unpaired electrons of the ureato fragments of 2 are resonance delocalized between the C-O, C-NPh, and C-NEt2 bonds, which are all partially doubly bonded.",
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T1 - Insertion reactions of phenyl isocyanate into hafnium nitrogen bonds

T2 - Synthesis and reactivity of hafnium complexes bearing substituted pyrrolyl ligands

AU - Hsieh, Kun Chun

AU - Lee, Wen Yi

AU - Lai, Chun Liang

AU - Hu, Ching Han

AU - Lee, Hon Man

AU - Huang, Jui Hsien

AU - Peng, Shie Ming

AU - Lee, Gene Hsing

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N2 - A bis(diethylamido)hafnium compound [C4(CH2NMe 2)-2]2Hf(NEt2)2 (1) has been prepared in 79% yield by reacting Hf(NEt2)4 with 2 equiv. of [C4H(CH2NMe2)-2] in heptane via deamination. Reacting compound 1 with 2 equiv. of phenyl isocyanate at room temperature in diethyl ether results in the PhNCO being inserted seletively into hafnium-NEt2 bonds to generate [C4(CH2NMe2)-2]2Hf[PhNC (NEt2)O]2 (2) in 56% yield. Similarly, while reacting 1 with 2 equiv. of phenyl isocyanate for a week in toluene produces a mixture of 2 and [C4(CH2NMe 2)-2]Hf[PhNC(NEt2)O]3 (3). For comparison, reacting Hf(NEt2)4 with 4 equiv. of PhNCO in a toluene solution at room temperature results in the PhNCO inserted into Hf-N bonds, and forms a tetrakis-ureato hafnium compound Hf[PhNC(NEt2)O]4 (4) in 88% yield. A theoretical calculation found that the unpaired electrons of the ureato fragments of 2 are resonance delocalized between the C-O, C-NPh, and C-NEt2 bonds, which are all partially doubly bonded.

AB - A bis(diethylamido)hafnium compound [C4(CH2NMe 2)-2]2Hf(NEt2)2 (1) has been prepared in 79% yield by reacting Hf(NEt2)4 with 2 equiv. of [C4H(CH2NMe2)-2] in heptane via deamination. Reacting compound 1 with 2 equiv. of phenyl isocyanate at room temperature in diethyl ether results in the PhNCO being inserted seletively into hafnium-NEt2 bonds to generate [C4(CH2NMe2)-2]2Hf[PhNC (NEt2)O]2 (2) in 56% yield. Similarly, while reacting 1 with 2 equiv. of phenyl isocyanate for a week in toluene produces a mixture of 2 and [C4(CH2NMe 2)-2]Hf[PhNC(NEt2)O]3 (3). For comparison, reacting Hf(NEt2)4 with 4 equiv. of PhNCO in a toluene solution at room temperature results in the PhNCO inserted into Hf-N bonds, and forms a tetrakis-ureato hafnium compound Hf[PhNC(NEt2)O]4 (4) in 88% yield. A theoretical calculation found that the unpaired electrons of the ureato fragments of 2 are resonance delocalized between the C-O, C-NPh, and C-NEt2 bonds, which are all partially doubly bonded.

KW - Insertion hafnium

KW - Phenyl isocyanate

KW - Pyrrolyl

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