Fluorinated bismuth alkoxides: from monomers to polymers and oxo-clusters

Abstract

A series of new bismuth fluoroalkoxide compounds have been prepared through the treatment of 1,1,1,3,3,3-hexafluoro-2-propanol with BiAr3 (where Ar=Ph, p-Tol). Reactions were conducted without the use of any additional solvent and the reaction products distilled or extracted with non-polar or polar Lewis base solvents. Structural analyses reveal that under variable reaction conditions the interaction of BiAr3 with (CF3)2CHOH can give a mixture of bismuth complexes with varying degrees of substitution, cluster formation and aggregation. Compounds [Bi(OCH(CF3)2)3(pyr)2] () (pyr=pyridine), [Bi(OCH(CF3)2)3(thf)3] () (thf=tetrahydrofuran), [Bi2(OCH(CF3)2)3(dabco)3] () (dabco=1,4-diazabicyclo[2.2.2]octane), [PhBi(OCH(CF3)2)2]n (), [Bi2O(OCH(CF3)2)4(C7H8)]2 () (C7H8=toluene), [Bi9O7(OCH(CF3)2)13] (), [Bi2O(OCH(CF3)2)4(Et2O)]2 (), [Bi2O(OCH(CF3)2)4(thf)]2 () and [Bi2O(OCH(CF3)2)4(tmeda)2] () (tmeda=N,N,N',N'-tetramethylethylenediamine) have been fully characterised including by single crystal X-ray diffraction.

Metal–Organic Derivatives with Fluorinated Ligands as Precursors for Inorganic Nanomaterials

“…The BiPh 3 reacted with hexafluoroisopropanol or hexafluoroacetylacetone to afford only the bissubstituted complexes "[PhBiL 2 ]" as the main product. 34,89 It was also possible to prepare a mixed hfac-TFA ligand complex.…”

“…34 The mononuclear [Bi(HFIP) 3 (py) 2 ] and mer-[Bi(HFIP) 3 (THF) 3 ] are simple adducts with 5-and 6-coordination numbers for the metal center, respectively, the latter being different from the previously known [Bi(HFIP) 2 (μ-HFIP)(THF)] 2 199,200 where each bismuth center is 5-coordinated and is connected to only one THF molecule. Another dinuclear complex [Bi 2 (HFIP) 6 2 )] n is a polymer with four coordinated bismuth centers bonded to a phenyl group and three alkoxy groups.…”

14. Solute–solvent interactions mediated by main group element(lone-pair)···π(aryl) interactions

“…The first three structures to be discussed, (24)- (27) The next four structures to be described, (27)- (30) (Figure 14.12), are tetranuclear bismuth(III) compounds. In bis(μ 3 -oxo)-tetrakis (μ 2 -1,1,1,3,3,3-hexafluoro-2-propoxo)-tetrakis(1,1,1,3,3,3-hexafluoro-2-propoxy)-tetra-bismuth(III) toluene solvate (27) [46], the cluster is situated about a centre of inversion. There are two distinct coordination environments for bismuth(III): the endocyclic atoms based on a O 5 donor set and the exocyclic bismuth(III) atoms, which are coordinated within a O 4 donor set.…”

Synthesis and structural characterisation of gallium and indium fluoroalkoxide ‘ate’ complexes

“…Fluorinated alcohols are another alternative source of ligand which have the potential to impart favourable properties when compared with their non-fluorinated analogues [10]. Recently, we described the synthesis and structural characterisation of a rich variety of bismuth fluoroalkoxides and oxo-clusters obtained from the treatment of BiAr 3 (Ar = Ph, p-Tol) with (CF 3 ) 2 CHOH [11]. On seeking to explore the related synthetic chemistry of the fluoroalkoxides of gallium and indium, a salt elimination approach was adopted as this had previously been reported to be successful in the synthesis of fluorinated and non-fluorinated alkoxides; Al(OCH(CF 3 ) 2 ) 3 was synthesised from AlCl 3 and Na(OCH(CF 3 ) 2 ) using reflux conditions and an excess of hexafluoroisopropanol [12] while a series of In(OR) 3 compounds have been prepared from the reactions of Gp 13 metal halides with non-fluorinated alkali metal alkoxides [13][14][15].…”

“…. .K1 4.1263(11), O1-In1-O2 90.42(13), O1-In1-Cl1 86.29(10), O2-In1-Cl1 91.26(11), O4-In2-O5 89.89(12), O5-In2-Cl2 90.07(9), O4-In2-Cl2 85.84(9), O1-K1-Cl1 63.72(7), O3-K1-Cl1 129.77(9), O4-K1-Cl1 110.82(8), O3-K1-O1 105.44(12), O3-K1-O4 99.58(12), O4-K1-O1 150.40(11). Symmetry operators: x, y, z and Àx, Ày, Àz.…”