Unprecedented Reaction Mode of Phosphorus in Phosphinidene Rare-Earth Complexes: A Joint Experimental–Theoretical Study

Abstract

Reactions of trinuclear rare-earth metal complexes bearing functionalized phosphinidene ligand [LLn(μ-Me)(μ-Me)(μ-η:η:η-PCH-o)] (L = [PhC(NCHPr-2,6)], Ln = Y (1a), Lu (1b)) with phenylacetylene, CO, diisopropyl carbodiimide, isocyanide, or PhSSPh lead to the formation of a series of phosphorus-containing products. The reaction of 1 with CS yields two novel P-methyl-phosphindole-2,3-dithiolate dianion complexes, revealing an unusual tandem desulfurization/coupling/cyclization reaction mode of CS. A possible reaction pathway was determined by density functional theory calculations. This emphasizes the key role of the reduction power of the formal P part of the phosphinidene in the C-S bond cleavage.

Synthesis and photophysical properties of rare earth (La, Nd, Gd, Y, Ho) complexes with silanediamido ligands bearing a chelating phenylbenzothiazole chromophore

“…Overall, the range of the bite angle values for a relatively small group of silanediamido complexes is quite narrow, which speaks for the poor plasticity of the N–Si–N fragment. For comparison, in a similar but larger family of amidinato complexes, the N–C–N bite angle changes from 106.1° in [{Y(L 1 )} 3 (μ 2 -Me) 2 (μ 3 -Me)(μ 3 -η 2 -DippNCP(C 6 H 4 ))] (L 1 = C(Ph)(NDipp) 2 − ) 50 to 125.7° in [Y(L 2 )(AlMe 4 ) 2 ] (L 2 = CH(N( o -Et 2 C 6 H 3 )) 2 − ) 51 with a mean value of 116.2°.…”

Activation of CS2 with the 2H-Phosphindole Complex to Construct P,S-Polycycles

“…The tandem desulfurization/coupling/ cyclization process provided a straightforward construction of 1-methyl-1H-phosphindole-2,3-dithiol rings. 11 The nucleophilic addition of the scandium phosphinidene complex to CS 2 gave interesting P,S-ligands and the corresponding Sc complexes. 12 However, to the best of our knowledge, the activation of CS 2 with carbon−phosphorus multiple bonds has never been achieved.…”

“…Maron, Zhou, and Zhang showed that the trinuclear rare-earth metal (Y or Lu) μ 2 -bridged phosphinidene complexes displayed interesting reactivity with CS 2 . The tandem desulfurization/coupling/cyclization process provided a straightforward construction of 1-methyl-1 H -phosphindole-2,3-dithiol rings . The nucleophilic addition of the scandium phosphinidene complex to CS 2 gave interesting P,S-ligands and the corresponding Sc complexes .…”

f-Element heavy pnictogen chemistry

“…Complex 27Lu exhibits Lu–P distances of 2.649(4)/2.644(4) Å, which is a similar range to that of the two shorter Lu–P bonds in 26Lu , whilst 27Y displays a range of Y–P distances [2.698(2)/2.692(2) Å] that are shorter than those seen for 26Y . The authors have additionally reported the crystal structure of the yttrium bridging phosphinidiide complex [{Y(PhC[NDipp] 2 )(μ-Me)} 2 (μ 3 -CCCPh)(μ,η 2 :η 3 -PC 6 H 4 )], 57 which exhibits Y–P bond distances of 2.701(3) and 2.700(3) Å; these are statistically indistinguishable from the corresponding distances seen in 27Y . However, the synthetic route and additional characterisation data for this complex have not been reported to date.…”