Organotitanium Fluorides as Matrices for Trapping Molecular ZnF2 and MeZnF

Abstract

Trapped as molecular solids, the transition metal fluorides ZnF(2) and MeZnF-the latter isolated for the first time-exist as adducts in [(Cp*TiF(3))(8)(ZnF(2))(3)] (1) and [(Cp*TiF(3))(4)(MeZnF)(2)] (2), respectively. Compounds 1 and 2 were obtained in reactions of [Cp*TiF(3)] (Cp*=C(5)Me(5)) with ZnMe(2) and Me(3)SnF in various molar ratios. The single-crystal structure of 1 is shown here; the unlabeled circles are F atoms.

Synthesis of Actinide Fluoride Complexes Using Trimethyltin Fluoride as a Mild and Selective Fluorinating Reagent

“…Although this compound forms a polymeric chain‐like structure of tin and fluorine atoms in the solid state, it has been shown to react with metal chlorides to generate metal fluorides and volatile trimethyltin chloride. [23b], [23c], Specifically, Me 3 SnF has been used to prepare a variety of alkaline‐earth (Mg, Ca, Sr), early (Sc, Y, Ti,[23a], , Zr,[23a], [30h], Hf,[23a], [31b], [31c], [31d], [31e] V, Nb, Ta), mid (W[30j], ), and late (Fe, Co, Zn) transition‐metal, main‐group (Al, Ga,[39g] Si,[23c], Ge, Sb, P[23b], ) and lanthanide‐metal (Sm, Ho, Er) organometallic and inorganic fluoride complexes.…”

18‐Crown‐6 and Titanium Tetrafluoride − Preparation of the TiIV Fluoride Crown Ether Complexes (TiF4)2(18‐Crown‐6) and the Stabilization of cis‐TiF4(H2O)2 in [{cis‐TiF4(H2O)2}2(18‐Crown‐6)]

“…of allylsilane is an effective catalyst for enantioselective addition of allylsilanes to aldehydes 10. In addition, titanium fluoride complexes have been extensively employed as complexing agents for LiF, NaF, MgF 2 , CaF 2 , Li 2 O, ZnF 2 , and preparation of hot‐guest compounds, e. g. (Cp*TiF 3 ) 4 CaF 2 , [(Cp*TiF 3 ) 8 (ZnF 2 ) 3 ] etc., which are soluble in organic solvents 11…”

Partially Fluorinated Rare Earth Metal Complexes

“…However, reactions between other complexes and Me 3 SnF are less well known. An interesting example is the oxidation of [Sm(C 5 H 4 t Bu) 2 (THF) 2 ] with Me 3 SnF for the preparation of [(C 5 H 4 t Bu) 2 Sm(μ‐F)] 3 ,9 or the reaction of CpTiF 3 and ZnMe 2 in the presence of Me 3 SnF 10. In general, since lanthanide‐fluorine bonds are very strong (124−135 kcal/mol for trivalent Eu, Yb, Er, Ho and Sm),11 the metathesis reaction of lanthanide complexes containing Cl, Br, I, SCN or Me ligands with trimethyltin fluoride under mild conditions seemed feasible.…”