933787-98-5Relevant academic research and scientific papers
Synthesis and structure of bulky phosphiniminato complexes of zirconium and hafnium: Aryl groups as non-innocent substituents in electrophilic systems
Said, Musa,Thornton-Pett, Mark,Hughes, David L.,Bochmann, Manfred
, p. 1354 - 1363 (2008/10/09)
Sterically highly hindered phosphiniminato complexes MCl3(NCP) were prepared from MCl4 and Li[NPC] in toluene [M = Zr or Hf; NPC = 4-ButC6H4C(SiMe3)P(Ph)2 {double bond, long}NC6H2Me3-2,4,6]. Reaction with methyl lithium readily affords the corresponding zirconium and hafnium trimethyl complexes. The structures of representative zirconium and hafnium complexes MX3(NPC) (X = Cl, M = Zr, Hf; X = Me, M = Hf) were determined by X-ray diffraction. In all cases the NPC ligand acts as C-N chelate, with an additional bonding contribution from the ipso-carbon atom of the C-bound aryl substituent, which results in a η1:η2-coordination mode. The reaction of the hafnium trimethyl complex with CPh3+ salts of perfluoroarylborate anions results either in the diastereoselective formation of the binuclear cation [{(NPC)HfMe2}2(μ-Me)]+ or in the formation of the mononuclear cation [(NPC)HfMe2]+, depending on the molar ratio of reagents.
