Oxidation and chalcogenylative disproportionation of anionic phosphide ligands in yttrium complexes with elemental sulfur and selenium

Abstract

Rare-earth mediated oxidation and disproportionation of anionic phosphide ligand has been established by the reactions of yttrium phosphide with S or Se, providing a potential route to synthesize rare-earth mono- and di-thio/selenophosphinates.

Synthesis, Structure, and Reactivity of Monoguanidinate Rare‐Earth Metal Aminobenzyl Enolate Complexes

“…After consideration of difference of coordination environment around metal center and metallic radii, the C(20)–P(2) bond length (1.855(4) Å) of µ‐ O(CH 2 ) 4 PPh 2 ligand is comparable to that of C–P bond in (C 5 H 5 ) 2 Lu[ µ ‐O(CH 2 ) 4 PPh 2 ] (1.847(4) Å) . The C(4)–P(1) distance (1.799(8) Å) of the terminal moiety O(CH 2 ) 4 PPh 2 is apparently shorter than the corresponding value in Tp Me2 CpYO(CH 2 ) 4 PPh 2 (1.838(8) Å) due to steric hindrance of big size Tp Me2 ligand …”

“…THF ring‐opening insertion M–P bonds have been proved successful synthetic strategy for the rare‐earth metal cyclopentadienyl butoxide complexes. [21b], [21f], And until now only very few reports concerning about the THF ring‐opening insertion M–P bonds involving non‐Cp lanthanide complexes appeared . In addition, the ring‐opening reactions of THF facilitated by low‐valent main group metals, late‐transition metals and classical Lewis acid‐base adducts were documented as well .…”

“…It is interesting that the four O(CH 2 ) 4 PPh 2 fragments in this molecular structure coordinate to Y atoms both in terminal and bridging coordination modes, instead of one of the two coordination patterns reported in literature. [21b], [21f], , The terminal Y–O distance (2.034(3) Å) and bridging Y–O–Y bond lengths (2.242(2) Å and 2.273(2) Å) in 8 are slightly shorter than those found in 4 due to greater steric hindrance around Y atoms in complex 8 . After consideration of difference of coordination environment around metal center and metallic radii, the C(20)–P(2) bond length (1.855(4) Å) of µ‐ O(CH 2 ) 4 PPh 2 ligand is comparable to that of C–P bond in (C 5 H 5 ) 2 Lu[ µ ‐O(CH 2 ) 4 PPh 2 ] (1.847(4) Å) .…”