Syntheses and structures of lanthanoid(ii) complexes featuring Sn–M (M = Al, Ga, In) bonds

Abstract

The reactions of the tris(pyridyl)tin(II) derivative [Li(thf)Sn(2-py(R))(3)] (py(R) = C(5)H(3)N-5-Me) (1) with the heavier group 13 alkyl compounds MEt(3), M = Ga or In, have been carried out. These led to formation of [{Li(thf)Sn(2-py(R))(3)}MEt(3)] adducts, which exhibit long Sn-M bonds and can be used for further lanthanoid metal coordination via the salt metathesis reaction with [Eu(Cp*)(2)(OEt(2))] (Cp* = η(5)-C(5)Me(5)) to give complexes [Eu{Sn(2-py(R))(3)MEt(3)}(2)]. In contrast, addition of the lighter group 13 analogue, (AlMe(3))(2), to 1 resulted in a pyridyl transfer reaction, yielding dimeric [AlMe(2)(2-py(R))](2). For comparison, the reaction of (AlMe(3))(2) with [Yb{Sn(2-py(R))(3)}(2)] (py(R) = C(5)H(3)N-3-Me) was explored, affording complex [Yb{Sn(2-py(R))(3)AlMe(3)}(2)]. All complexes have been characterised by NMR spectroscopy and X-ray crystallographic studies.

Monoanionic Tin Oligomers Featuring Sn–Sn or Sn–Pb Bonds: Synthesis and Characterization of a Tris(Triheteroarylstannyl)Stannate and -Plumbate

“…However, this molecule, which could neither be isolated nor detected, may have then reacted further with another equiv of 1 to give the lithium complexes 2 or 3, respectively, by virtue of a donor-acceptor interaction between two low valent group 14 element species. This may be explained with the less steric requirement of the pyridyl ligand as well as the pronounced two-electron donor ability of 1 comparable to other tris(2-pyridyl)stannates [22][23][24]. …”

“…However, this molecule, which could neither be isolated nor detected, may have then reacted further with another equiv of 1 to give the lithium complexes 2 or 3, respectively, by virtue of a donor-acceptor interaction between two low valent group 14 element species. This may be explained with the less steric requirement of the pyridyl ligand as well as the pronounced two-electron donor ability of 1 comparable to other tris(2-pyridyl)stannates [22][23][24]. Indeed, the molecular structures of complexes 2 and 3 ( Figure 1, Table 1) imply the donation of a lithium stannate fragment to the central element(II) atom of a E{Sn(2-py 6OtBu )3}2 molecule due to the intramolecular N-coordination of the lithium cation by only one tris(2-pyridyl)stannyl unit in 2 and 3 as found for previously reported tris(2-pyridyl)stannate complexes [22][23][24][25].…”

“…Our studies on related triheteroaryltin(II) compounds revealed a diverse reactivity. Thereby, it was found that compounds [Li(THF)Sn(2-py R ) 3 ] (py R = C 5 H 3 N-5-Me or C 5 H 3 N-3-Me), in which the lithium cation is well embedded within the tris(pyridyl)stannate core, can either act as a two-electron donor leading to a tin-element bond formation [22,23] or may be used for salt metathesis reactions with the lone pair of electrons at the tin(II) atom remaining available [24]. …”

A new approach to predict the formation of 3D hybrid organic‐inorganic perovskites

“…Nevertheless, these compounds are reported to form perovskite experimentally but their value of TF is lying outside the reported range. In contrary, some of the ABX 3 combinations are mainly reported as non‐perovskite but their value of TF is lying within the reported range (0.8 to 1.0) (NH 4 GeCl 3 [TF = 0.91], NH 4 GeBr 3 [TF = 0.90], and NH 4 GeI 3 [TF = 0.88]). Therefore, TF is just a necessary condition to know that an ABX 3 combination will form a 3D perovskite structure or not.…”

“…Thus, the TF and μ alone or in combination do not fully capture the prerequisites for the formation of the HOIPs structure. It could be mainly due to the following facts which have not been given due consideration in the previous studies The main challenge to predict the formation of HOIPs structure using TF is to determine the exact ionic radii of the cations and anions.…”