有機合成化学協会誌
Online ISSN : 1883-6526
Print ISSN : 0037-9980
ISSN-L : 0037-9980
4族遷移金属アミド錯体の化学
羽村 敏永島 英夫
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1999 年 57 巻 8 号 p. 698-707

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In this article are summarized general properties, synthesis, reactivity, and catalysis of Group 4 transition metal amide complexes. Thermally robust but moisture sensitive compounds of the type M (NR2) 4 and MYn (NR2) 4-n CM = Ti, Zr, Hf ; R =H, alkyl, aryl ; Y = X (halogens), OR ; n=1-3) are generally synthesized from MX44 and amines or alkali metal amides, by disproportionation reactions of M (NR2) 4 with MY4, or by ligand exchange reactions of M (NR2) 4 and MYn (NR2) 4-n. Since nitrogen atoms in these compounds form both u- and it-donor bonds to the metal center, the amide complexes typically have planar MNR2 units with shorter M-N lengths.
The amide complexes are highly reactive towards carbonyl compounds or Brønsted acids such as cyclopentadiene. These reactions are useful for chemical transformation of carbonyl compounds and synthesis of metallocene derivatives ; some of the latter are excellent catalysts for olefin polymerization.
Besides metallocene derivatives, Group 4 transition metal amide complexes themselves have recently received much attention as catalysts for ethylene and α-olefins and for hydroamination of acetylenes.

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