Hafnium alkyl complexes of the anionic PNP pincer ligand and possible alkylidene formation

Abstract The diarylamido-based PNP pincer ligand can be used successfully for support of organometallic Hf complexes (PNP = [(4-Me-2- i Pr 2 P–C 6 H 3 ) 2 N]). (PNP)HfCl 3 ( 3 ) was prepared via reaction of (PNP)Li ( 2 ) with HfCl 4 (OEt 2 ). Reactions of (PNP)HfCl 3 with alkyl Grignards led to triple alkylation to produce (PNP)HfMe 3 ( 4 ) with a small methyl or only double alkylation to give (PNP)Hf(CH 2 SiMe 3 ) 2 Cl ( 5 ) with a larger alkyl. Structures of 3 , 4 , and 5 in the solid state were established by X-ray diffraction studies. Structures of the alkyl complexes 4 and 5 display remarkably irregular coordination environments about Hf, while in 3 it is approximately octahedral. Compound 4 was found to be thermally stable at 75 °C. On the other hand, thermolysis of 5 at similar conditions led to a mixture of products, the major one of which is believed to be a Hf alkylidene on the basis of in situ NMR spectroscopic observations (e.g., δ 248.2 ppm in the 13 C{ 1 H} NMR spectrum).