Zirconium and Hafnium Hydrazinediido Half-Sandwich Complexes: Synthesis and Reactivity

Abstract

The hydrazinediido complexes [Cp*M(N xyl N)-(NNPh 2 )(dmap)] (M = Zr, 3a; M = Hf, 3b; N xyl N = 2-(Nxylylamino)pyrrolinate) have been synthesized, and their reactivity has been investigated. Both complexes were prepared from [Cp*M(N xyl N)Cl 2 ] (1a,b) and [Cp*M(N xyl N)-(NHNPh 2 )Cl] (2a,b), respectively, as precursors. While 3a was obtained by dehydrohalogenation of 2a using LiHMDS in the presence of dmap, reaction of 2b with LiHMDS

Synthesis of an Arenide-Masked Scandium Complex Accom-panied by Reductively Induced C-H Activation

“…Though unprecedented for scandium, dianionic guanidinate-supported early transition metal complexes are known and exhibit bond metrics similar to those observed in Sc C-H •Et2O. [33][34][35][36][37][38][39][40] The formation of the Sc-C bond and the dianionic guanidinate can be explained via hydride migration from a C-H bond of the isopropyl group to the imine carbon of the ketimine backbone. The presence of the t Bu2C(H)-proton has been confirmed by 1 H NMR spectroscopy, appearing as a singlet at 3.44 ppm in C6D6.…”

Synthesis of an Arenide Scandium Complex Accompanied by Reductively Induced C–H Activation

“…Altogether, the parameters point to the presence of a dianionic guanidinate ligand where both coordinating nitrogen atoms (N4 and N6) possess formal negative charges. Though unprecedented for scandium, dianionic guanidinate-supported early-transition-metal complexes are known and exhibit bond metrics similar to those observed in Sc C–H ·Et 2 O …”