From a nanoparticular solid-state material to molecular organo-f-element-polyarsenides

Abstract

Reaction of non-classical divalent lanthanide compounds with nanoparticulate gray arsenic via three- and four-electron reduction led to a series of new f-element polyarsenides, including the largest f-element polyarsenide known to date.

f-Element heavy pnictogen chemistry

“…Very recently, the authors expanded this chemistry, reacting nano -As 0 with the dilanthanide inverted arene complexes [K(18-crown-6)][{Ln(Cp′′) 2 } 2 (μ-η 6 :η 6 -C 6 H 6 )] (Ln = La, Ce) and [[K(18-crown-6)] 2 [{Ln(Cp′′) 2 } 2 (μ-η 6 :η 6 -C 6 H 6 )] (Ln = Ce, Nd) to give a range of lanthanide Zintl anions 96–99 containing As 3 3− , As 7 3− , and As 14 4− ligands, respectively, that were previously not accessible in molecular lanthanide chemistry, Scheme 30 . 129 The As 14 4− unit in 97 is the largest organo-lanthanide-polyarsenic complex to date. The synthesis and characterisation of these diverse polyarsenic lanthanide complexes demonstrated the great utility of nano -As 0 for accessing novel molecular polyarsenic clusters.…”

Neutral inverse-sandwich rare-earth metal complexes of the benzene tetraanion

“…1). [14][15][16][17] In addition, Mazzanti and co-workers reported quadruple-decker cerium and triple-decker samarium toluene-bridged complexes, both containing toluene dianion(s). 18,19 While rareearth metal complexes of the parent benzene tetraanion remain elusive, Diaconescu and Huang reported a series of rareearth metal biphenyl complexes [K(solvent)] 2 [[(NN TBS )M] 2 (mh 6 ,h 6 -C 6 H 5 Ph)] (NN TBS = fc(NSi t BuMe 2 ) 2 , fc = 1,1 0ferrocenediyl; M = Sc, Y, La, Lu, Gd, Dy, Er, Sm), featuring a mh 6 ,h 6 -bound biphenyl tetraanion with most negative charges localized at the bound ring (II, Fig.…”

“…13 More recently, Evans and Roesky reported synthesis and structural characterization of several closely relevant inverse-sandwich rare-earth metal benzene complexes [K (18-crown-6)]n[(X2Ln)2(μ-η 6 ,η 6 -C6H6)] (n = 1 or 2; X = Cpʺ or Cpʹ, Cpʹ = η 5 -C5H4(SiMe3); Ln = La, Ce, Nd), which contain benzene monoanion or dianion (I, Figure 1). [14][15][16][17] In addition, Mazzanti and co-workers reported a quadruple-decker cerium and a triple-decker samarium toluene-bridged complexes, both containing toluene dianion(s). 18,19 While rare-earth metal complexes of the parent benzene tetraanion remain elusive, Diaconescu and Huang reported a series of rare-earth metal biphenyl complexes [K(solvent)]2[[(NN TBS )M]2(μ-η 6 ,η 6 -C6H5Ph)] (NN TBS = fc(NSi t BuMe2)2, fc = 1,1ʹ-ferrocenediyl; M = Sc, Y, La, Lu, Gd, Dy, Er, Sm), featuring a μ-η 6 ,η 6 -bound biphenyl tetraanion with most negative charges localized at the bound ring (II, Figure 1).…”