Monomeric Sn(ii) and Ge(ii) hydrides supported by a tridentate pincer-based ligand

Abstract

Herein we report the syntheses of terminal Sn(II) (3) and Ge(II) (4) hydrides from the corresponding chloride precursors [{2,6-iPr(2)C(6)H(3)NCMe}(2)C(6)H(3)MCl] (M = Sn (1), Ge (2)) using [K{B(sec-Bu)(3)}H] as a hydrogenating agent. Combination of steric shielding and intramolecular N → M interactions resulted in the protection of M(II)-H bonds.

Bis‐Sulfonyl O,C,O‐Chelated Metallylenes (Ge, Sn) as Adjustable Ligands for Iron and Tungsten Complexes

“…This is in contrast with the structure of the previously described stannylene E , in which the flanking tolyl groups are situated on the same side of the central ring (Figure ) . The Group 14 elements (Ge and Sn) are four coordinated and, considering the lone pair of electrons, exhibit a distorted seesaw geometry . A value of 77.95(5)° is observed for the C1‐Ge1‐O1 angle and 73.99(3)° for the C1‐Sn1‐O1 due to the formation of five‐membered rings by coordination of the sulfonyl groups to the germanium or tin atoms.…”

A nitrogen-base catalyzed generation of organotin(ii) hydride from an organotin trihydride under reductive dihydrogen elimination

“…25 , 30 The observed coupling constant is in accord with the coupling in related tricoordinate organotin( ii ) hydride complexes with terminal Sn–H bond such as found in the carbene adduct Ar*SnH(NHC) (223 Hz) 24 and diketiminate/pincer complexes E and F (64/112 Hz). 39 , 41 …”

The Role of Monoanionic Aryl Pincer Ligands in the Stabilization of Group 14 Metallylenes

“…The first examples for N,C,N-pincer ligand stabilized divalent germanium derivatives were presented by Bibal et al, with diethylaminomethyl groups as ortho substituents (L I ), obtained through the reaction of 2,6-bis(dialkylaminomethyl)-phenyl bromide (alkyl = Et, i-Pr) with n-BuLi then reaction with GeCl2•dioxane, as shown in Scheme 3. [17,18] Similar methods were used to obtain the imino-based N,C,N-pincer ligand (L II ) stabilized chlorogermylenes too, starting from N,N'-bis-(2,6diisopropylphenyl)-2-bromo-isophthalaldimine, [19] 2,6-bis[N-(2',6'-diisopropylphenyl)ketimino]phenyl-1-bromide [20] or bis(N-tert-butyl)-2-bromoisophthalaldimine. [21] NR 2 presented in the literature were synthesized by adding n-BuLi to 1,3-bis{(4-methylphenyl)sulfonyl}-5-tert-butylbenzene (L V ) [22] or LDA to 1-(p-tolylsulfinyl)-3-tosyl-5-tert-butyl-benzene (L VI ) [23] in order to obtain the corresponding carbanions, which in reaction with GeCl2•dioxane led to the desired germylenes 6 and 7, as shown in Scheme 3.…”