Publisher Summary This chapter discusses the perchlorate ion complexes. Coordination of perchlorate to transition and nontransition metal ions has been well established, though in most of the cases the metal-perchlorate bond is rather weak and has been termed as “semicoordination”. The highly symmetrical perchlorate ion is a hard base and falls into the category of relatively nonpolarizable and noncoordinating anions such as BF 4 ˉ and PF 6 ˉ. Its ability to coordinate strongly to soft metal ions is therefore limited. When coordination does occur, the perchlorate group may be linked to a metal ion in a monodentate and/or bidentate manner through oxygen atoms; the latter linkage can be either chelating. X-ray crystal structure analysis has unequivocally established coordination of perchlorate in a number of perchlorate complexes.

Perchlorate Ion Complexes

Zinc and cadmium

Guanine complexes with dysprosium(III), thorium(IV) and uranium(IV) chlorides

Inhibiting effect of phosphorus compounds on model transesterification and direct esterification reactions catalysed by titanium tetrabutylate: 2

Three-dimensional sodium phosphinates derived from a bis-functionalized phosphinic acid

Triethyl phosphonoformate (tepf) reacts with metal chlorides at elevated temperatures to yield ethyl chloride and the corresponding M(depf)n complexes (depf=diethyl phosphonoformato ligand; Mn+=Dy3+, Ti3+, V3+, Cr3+, Fe3+, Th4+, U4+). The depf ligand is in the tautomeric form, arising by elimination of one of the -P(OC2H5)2 ethyl groups. The new metal complexes are linear chainlike polymeric species, involving bidentate bridging depf ligands coordinating through the two POO oxygens to adjacent metal ions; the COO oxygens do not participate in coordination. The ambient temperature magnetic moments of several of the paramagnetic M(depf)n complexes (M=Ti3+, V3+, Cr3+, U4+) are subnormal, as would be expected for linear chainlike polymeric metal complexes. AlCl3 .6H2O reacts with tepf to yield a different complex, namely Al(ehp)3 (ehp=ethyl hydrogenphosphonate, (C2H5O)HPOO−). Initial formation of Al(depf)3, followed by hydrolytic elimination of the -COOC2H5 ethyl group, with the P-H bond being eventu...

Polymeric complexes formed by reaction of triethyl phosphonoformate with metal chlorides

A series of methylphenylphosphinate {mpp; [-O-P-Ph(Me)-O-]−} complexes of the forms M(mpp)3 (M = Al, Ga, In, Sc, Y, Dy, Ti, V, Cr and Fe) and M(mpp)4 (M = Th or U) were made from the appropriate metal chloride and a large excess of MeO(Me)PhP(O) at elevated temperatures. Structures involving linear, ligand-bridged polymeric species are suggested on the basis of the i.r. and magnetic data.

Richard Rabin

Papers

Polymeric complexes formed by reaction of triethyl phosphonoformate with metal chlorides

Methylphenylphosphinate complexes with tri- and tetra-positive metal ions

Poly(metal methylphenylphosphinates) from metal chloride solutions in methyl methylphenylphosphinate

Well-defined adducts of triethyl thiophosphate with some metal perchlorates

Tris(diethylthiophosphato)aluminum(III)