Polysulfide Coordination Clusters of the Lanthanides

Abstract

The reaction of [(DippForm) Ln(thf) ] with an excess of elemental sulfur in toluene resulted in the formation of the trinuclear polysulfide coordination clusters [(DippForm) Ln S ] (Ln=Sm, Yb; DippForm=N,N'-bis(2,6-diisopropylphenyl)formamidinate). These are the first f element coordination clusters (Ln S ) with a larger polysulfide unit (n and x>2). The formation of the coordination clusters can be rationalized by the reductive cleavage of S with divalent lanthanides.

Trapping CS22– and S32– between Two Ytterbium Formamidinates

“…28 Roesky et al recently reported that under their experimental conditions, treatment of 1aYb with excess sulfur in toluene with heating, produced the tetra-sulfide species, along with DippFormH (suggested to occur from a radical induced mechanism). 18 It is likely that our more mild conditions and rapid isolation hindered the formation of the tetra-sulfide and permitted the isolation of potential precursors, e.g., (S 2 )/(S 3 ), where additional S insertion would lead to the tetra-sulfide and concomitant products. It is clear from the isolation of 5 (which also contains DippFormH) and the difficulty in isolating pure 4 that the redistribution process which yields the tetra-sulfide is likely in progress.…”

“…18,26 The most recent example also utilized DippForm coligands. 18 There are a few examples of actinide trisulfides, 27 obtained by oxidation of trivalent precursors with elemental S. One remarkable example was a species which contained both di-and trisulfide ligands -both in full occupancy which was achieved using siloxide coligands, namely, {[KU(OSi(OtBu) 3 ) 3 ] 2 (μ-S 2 )(μ-S 3 )}. 27a The S−S−S bond lengths and bond angles in 4 (Figure 2) are larger than those observed in the tetra-sulfide complex [Yb 3 (DippForm) 3 (μ-S 4 ) 3 ] (S−S−S−S range: 1.913(4)− 2.093( 18) Å, with S−S−S bond angles of: 100.79(8), and 102.27(9)°), 18 probably owing to the difference in coordination of the S 4 unit (which is μ-1κ(S,S″,S‴):2κ-(S,S′,S⁗) 17 versus the μ-1κ(S,S′):2κ(S′,S″) coordination in 4.…”

3d–4f heterometallic complexes by the reduction of transition metal carbonyls with bulky LnII amidinates

“…By using different electronic and steric environments around divalent lanthanide elements, a different reactivity can be achieved with a same substrate. [37][38][39][40][41][42][43][44][45] 42 In addition, activation of white phosphorous and yellow arsenic by [(DippForm) 2 Sm II (thf ) 2 ] led to the formation of [{(DippForm) 2 Sm III } 2 (μ-η 4 -Pn 4 )] (Pn = P, As). 43 These products contrast with the cage-type molecules [{Cp* 2 Sm III } 4 (Pn) 8 ] (Pn = P, 37 As, 44 and Sb 47 ) that were obtained by reaction of [Cp* 2 Sm II ] with white phosphorous, nanoscale arsenic, and nanoscale antimony, respectively.…”

Tandem Silver Cluster Isomerism and Mixed Linkers to Modulate the Photoluminescence of Cluster‐Assembled Materials

“…Atom-precise metal chalcogenolate nanoclusters [1][2][3][4][5][6][7][8] are an ew category of materials with many unusual properties, the most important of which is luminescence. [5] Among them, low-cost Ag chalcogenolate clusters (SCCs) [1a-f,2b-e,4] remain largely unexplored in contrast to Au thiolate clusters,a nd currently their structure-luminescence correlations are poorly understood.…”