Hydrolysis of C,N‐chelated diorganotin(IV) chlorides and catalysis of transesterification reactions

Abstract

Diorganotin(IV) dichlorides of formula L

Direct Synthesis of Two-Dimensional SnSe and SnSe2 through Molecular Scale Preorganization

“…The methyl groups of each ligand are located on the same coordination hemisphere and point toward each other to minimize the steric repulsion due to the lone pairs located on each Se atom. The Sn–Se bond distances in 1 were found to be in the range of 2.5526(6)–2.5964(7) Å, which corresponded well to values reported for organic selenolate ligands bonded to a Sn IV center (2.52–2.68 Å). ,− The Sn–N bond length of 2.581(3)–2.597(5) Å for complex 1 is elongated, when compared to published data ranging between 2.27 to 2.50 Å. ,,− In comparison to those of the [Sn­(SC 2 H 4 N­(Me)­C 2 H 4 S) 2 ] and [Sn­(SC 2 H 4 N­(Et)­C 2 H 4 S) 2 ] complexes with a Sn–N bond length in the range 2.52–2.57 Å, the slight elongation of bond lengths reflects the weakening of the Sn–N bonds due to the greater donor strength of the thiolate and selenolate ligands. For complex 3 , the chalcogen atoms were indistinguishable and the solid-state structure was modeled by a 0.5/0.5 S/Se occupation for every position.…”

“…Partially substituted chloride complex [SnCl 2 (SeC 2 H 4 (Me)­NC 2 H 4 Se)] ( 2 ) showed the tin center is coordinated by two chlorido ligands and one tridentate aminoselenolate ligand in a distorted trigonal bipyramidal geometry (Figure c). The Sn–Se bond length [2.4976(3) Å] is slightly shorter than the average value reported in the literature (2.52–2.68 Å). ,− The Sn–N bond length of 2.3506(19) Å corresponded well with the literature values (2.28–2.50 Å). ,,− Tables with atomic coordinates, bond lengths and angles, and torsion angles can be found in Tables 2–10 of the Supporting Information.…”

Hypercoordination by Multiple Dangling Benzylmethoxy Ligands in Highly Crowded Triaryltin Bromide [(2‐MeOCH2C6H4)]3SnBr and Diaryltin Mixed Halides [(2‐MeOCH2C6H4)]2SnBrCl, and a related Distannane and Distannoxane

“…[24] The SnÀ C bond distance of 2.166 Å is also in the middle range of SnÀ C bond distances of other distannanes [22][23][24] Due to the use of SnCl 4 as a reagent in the synthetic pathway, compound 4, [{2-(MeOCH 2 )C 6 H 4 )} 2 SnBr] 2 O, also shows a composition with a Br/Cl mixture 64/36. Similar distannoxane compounds have been reported earlier: (μ-oxo)-dichlorotetrakis(2-(phenylazo)phenyl)-tin, [25] (μ 2 -oxo)-bis(N,N-dimethyl-1phenylmethanamine)-dichloro-di-phenyl-di-tin(iv), [26] (μ 2 -oxo)tetrakis(2-[(dimethylamino)methyl]phenyl)-dichloro-di-tin, [27] and (μ 2 -oxo)-bis(bis(2,4,6-tris(trifluoromethyl)phenyl)-chloro- tin(iv)). [28] In these distannoxanes the SnÀ OÀ Sn angle ranges from 137°to 144°, thus the Sn-OÀ Sn angle in 4 of 148.1(2)°is the largest to date, Figure 5a.…”