Neutral and Cationic Organoaluminum Complexes Utilizing a Novel Anilido-Phosphinimine Ancillary Ligand

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• 作者：Gregory C. Welch ; Warren E. Piers ; Masood Parvez ; and Robert McDonald
• 刊名：Organometallics
• 出版年：2004
• 出版时间：April 12, 2004
• 年：2004
• 卷：23
• 期：8
• 页码：1811 - 1818
• 全文大小：241K
• 年卷期：v.23,no.8(April 12, 2004)
• ISSN：1520-6041

文摘

A new chelating N,N ligand family incorporating an anilido-phosphinimine donor set hasbeen designed and an example prepared in multigram quantities in three steps using aconvenient, modular synthetic approach. The ligand 1-(NHAr)-2-(PPh₂=NAr')C₆H₄ (1·H; Ar= 2,6-ⁱPr₂-C₆H₃; Ar' = 2,4,5-Me₃C₆H₂) was prepared in three steps in a 30-35% overall yieldand was fully characterized in its protio form as well as in the form of its lithium salt, 1·Li.In both compounds, the donor array assumes a conformation in which the P=N moiety dipsout of the plane formed by the four atoms in the rigid ortho-disubstituted aryl ring of theligand backbone. The coordinating properties of the new ligand were demonstrated by thesynthesis of some organoaluminum derivatives. The monomeric compounds LAlMe₂ (2) andLAlH₂ (3) were prepared by the reaction of 1·H with AlMe₃ and AlH₃·NMe₃, respectively,and were fully characterized by NMR spectroscopy and X-ray crystallography. Cationicderivatives were formed by activation of 2 and 3 with either B(C₆F₅)₃ or [Ph₃C]⁺[B(C₆F₅)₄]^-.All of the neutral and cationic compounds qualitatively exhibited high levels of stability incomparison to related organoaluminum compounds, illustrating the exemplary steric andelectronic properties of the new ligand system.