Franceschini Pier Luigi, Morstein Marcus, Berke Heinz, Schmalle Helmut W
Anorganisch-Chemisches Institut der Universität Zürich, and Department of Materials, Laboratory for Surface Science and Technology, ETH Zürich, Switzerland.
Inorg Chem. 2003 Nov 3;42(22):7273-82. doi: 10.1021/ic034328f.
An amine elimination pathway has been used to produce a number of homo- and heteroleptic zirconium complexes, starting from tetrakis(dialkylamido)zirconium complexes and beta-diketimine or, alternatively, Schiff Base compounds. Reaction of 2 equiv of the bidentate beta-diketimine (2Z,4E)-N-methyl-4-(methylimino)pent-2-en-2-amine with Zr(NR(2))(4) (R = Me, Et) affords the six-coordinate heteroleptic compounds bis(N-methyl-4-(methylimino)pent-2-en-2-amido)bis(dialkylamido)zirconium 1 (alkyl = Me) and 2 (alkyl = Et). The dynamic behavior of these two compounds in solution has been investigated. Reaction with the isopropyl-substituted beta-diketimine (2Z)-N-isopropyl-4-(isopropylimino)pent-2-en-2-amine gives the five-coordinate mono(diketiminato)-substituted compound (N-isopropyl-4-(isoropylimino)pent-2-en-2-amido)tris(dimethylamido )zirconium, 3. With employment of the Schiff base (3Z)-4-(methylamino)pent-3-en-2-one, it was also possible to prepare the six-coordinate bis(4-(methylamino)pent-3-en-2-onato)bis(diethylamido)zirconium compound 4. When the bidentate ligand bearing hydrogen as substituent on the imino-nitrogen atom was employed, homoleptic tetrakis(beta-ketoiminato)- and tetrakis(beta-diketiminato)zirconium compounds 5 and 6 can be obtained. Complexes 1 and 5 have been tested for their air stability with reference to Zr(NMe(2))(4). The stability order turned out to be 1 > 5 >> Zr(NMe(2))(4). The thermal properties and volatility of all the compounds are discussed in view of their potential application in metal-organic chemical vapor deposition processes (MOCVD) of zirconium nitride.
一种胺消除途径已被用于从四（二烷基氨基）锆配合物和β - 二酮亚胺或席夫碱化合物出发制备多种均配和异配锆配合物。2当量的双齿β - 二酮亚胺（2Z，4E）-N - 甲基 - 4 - （甲基亚氨基）戊 - 2 - 烯 - 2 - 胺与Zr（NR₂）₄（R = 甲基，乙基）反应得到六配位异配化合物双（N - 甲基 - 4 - （甲基亚氨基）戊 - 2 - 烯 - 2 - 酰胺基）双（二烷基氨基）锆1（烷基 = 甲基）和2（烷基 = 乙基）。研究了这两种化合物在溶液中的动态行为。与异丙基取代的β - 二酮亚胺（2Z）-N - 异丙基 - 4 - （异丙基亚氨基）戊 - 2 - 烯 - 2 - 胺反应得到五配位单（二酮亚胺基）取代化合物（N - 异丙基 - 4 - （异亚丙基亚氨基）戊 - 2 - 烯 - 2 - 酰胺基）三（二甲基氨基）锆，3。使用席夫碱（3Z）-4 - （甲氨基）戊 - 3 - 烯 - 2 - 酮，也能够制备六配位双（4 - （甲氨基）戊 - 3 - 烯 - 2 - 酮基）双（二乙氨基）锆化合物4。当使用在亚氨基氮原子上带有氢作为取代基的双齿配体时，可以得到均配的四（β - 酮亚氨基）锆和四（β - 二酮亚氨基）锆化合物5和6。参照Zr（NMe₂）₄测试了配合物1和5的空气稳定性。稳定性顺序为1 > 5 >> Zr（NMe₂）₄。鉴于它们在氮化锆的金属有机化学气相沉积过程（MOCVD）中的潜在应用，讨论了所有化合物的热性质和挥发性。
