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 language | English |
|---|---|
| Pages (from-to) | 3362-3369 |
| Number of pages | 8 |
| Journal | Journal of Organometallic Chemistry |
| Volume | 689 |
| Issue number | 21 |
| DOIs | |
| Publication status | Published - 2004 Oct 15 |
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All Science Journal Classification (ASJC) codes
- Biochemistry
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
- Materials Chemistry
Cite this
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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 journal › Article
TY - JOUR
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
PY - 2004/10/15
Y1 - 2004/10/15
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.
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U2 - 10.1016/j.jorganchem.2004.07.046
DO - 10.1016/j.jorganchem.2004.07.046
M3 - Article
VL - 689
SP - 3362
EP - 3369
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 21
ER -