Synthesis and stereochemistry of reactive mono(amido phosphine) derivatives of zirconium(IV) and hafnium(IV). X-ray crystal structures of fac-HfCl3[N(SiMe2CH2PMe2)2] and mer-ZrCl3[N(SiMe2CH2P(CHMe2)2)2]

Abstract

Synthesis and Stereochemistry of Reactive Mono(amido phosphine) Derivatives of Zirconium(IV) and Hafnium(IV). X-ray Crystal Structures of fac-HfCl3[N(SiMe2CH2PMe2)2] and mer-ZrCl3[N(SiMe2CH2P(CHMe2)2)2]

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

“…The longest HfeP distances were found in 5 which probably reflects the increased steric pressure from the larger alkyl groups, as well. This trend and the approximate values are reminiscent of Fryzuk's (P 2 N 2 )HfX 2 [26] and and ( Si PNP Me )HfX 3 [17,27] complexes where for X ¼ Cl, the HfeP distances (ca. 2.7 Å) were ca.…”

Zirconium complexes containing a diarylamido diphosphine ligand: Structural preferences controlled by ligand electronics and sterics

“…Notably, the terminal chlorides lie closer to zirconium by 0.236 Å (average) than the bridging ones. It is of particular interest to compare the structures of binuclear {[PNP] ZrCl 2 (mÀCl)} 2 and mononuclear ZrCl 3 [N(SiMe 2 CH 2 P i Pr 2 ) 2 ] [37]. Though both amido diphosphine ligands bind to zirconium in a meridional fashion and ZreN, ZreP, and ZreCl(terminal) distances are all comparable, the PeZreP angle in the former (137.1(1) ) is markedly smaller than that in the latter (159.38(4) ), consistent with the discrepancy in coordination number of these species.…”

Pincer Complexes of Lithium, Sodium, Magnesium and Related Metals: A Discussion of Solution and Solid-State Aggregated Structure and Reactivity

“…The resulting formally anionic amidos have revealed a rich and diverse coordination chemistry with early, middle and late transition metal centres in addition to complexation with a vast array of lanthanide and main group elements [93]. Although the lithium materials have been used for some time, the attempted characterisation of these species in the solid state has been thwarted by the lack of material suitable for X-ray analysis [93][94][95]. The materials do form crystalline adducts with other Li species however (this is detailed in Sect.…”