Hydrogen abstraction from organotin di- and trihydrides by N-heterocyclic carbenes: a new method for the preparation of NHC adducts to tin(ii) species and observation of an isomer of a hexastannabenzene derivative [R₆Sn₆]

Abstract

N-Heterocyclic carbenes are shown to cleanly abstract dihydrogen from organotin di- and trihydrides to intermediately form the reactive stannylene species [R2Sn] and [R′SnH], respectively, which undergo further reactions.

Group 14 inorganic hydrocarbon analogues

“…73c, 86 Inoue and Eisenhut synthesized the donor-stabilized hydrido(silyl)silene adduct ImMe 4 ÁSi(H)Si t Bu 3 (17) ImMe 4 = [(MeCNMe) 2 C:] via the base-induced dehydrohalogenation of the halogenated precursor ClSiH 2 (Si t Bu 3 ) (16) (eqn (15)). 88 Notably the latter two syntheses highlight the ability of N-heterocyclic carbenes to act as dehydrohalogenation and dehydrogenation agents within the main group. 88 Notably the latter two syntheses highlight the ability of N-heterocyclic carbenes to act as dehydrohalogenation and dehydrogenation agents within the main group.…”

Dimeric platinum–stannylene complexes by twofold ligand transfer from an NHC adduct to an organotin(ii) hydride

“…1 Distannene complexes with strong Sn-Sn interaction of two R 2 Sn moieties within the metal coordination sphere have been reported more recently. 6 When trip 2 Sn(NHC) was reacted with 0.5 equivalents of zero-valent nickel triad precursors [ML 2 ] [M = Ni, Pd, Pt, L = Pt-Bu 3 , PCy 3 , cod] formation of distannene complexes [(NHC) 2 M(Sn 2 trip 4 )] was observed. 4 Since the number of formally accessible orbitals at the Sn site is augmented in this class of compounds (for L 0 = monodentate), depending on the electronic situation of the metal fragment triple bonding toward the group 14 centre can be realized.…”

Reductive Elimination of Hydrogen from Bis(trimethylsilyl)methyltin Trihydride and Mesityltin Trihydride

“…In the solid‐state structure the two stannyl tin atoms Sn2 and Sn3 are separated by 2.8417(3) Å and the bonds with the stannylene tin atoms Sn1−Sn2 and Sn3−Sn4 (2.8938(3), 2.9022(3) Å) are slightly longer. These distances can be compared with Sn−Sn distances found in stannyl stannylenes [published range: 2.81531(17)–2.9688(5)] and distannanes [published range: 2.692(1)–3.034(1)] and are expected for single bonds between tin atoms . The sum of angles at the Sn1 and Sn4 atoms of 296.0 and 296.5° are in line with a lone pair residing on these atoms.…”

“…As a major result of these investigations we can summarize that the composition of the product is controlled by both the number of equivalents of N‐heterocyclic carbene base and the size of the substituent R present at the organotin trihydride RSnH 3 . Furthermore, the hydrogen elimination induced by carbene or nitrogen bases leads to tin molecules with tin in oxidation states varying between Sn III and Sn 0 . Thus, distannanes, stannyl stannylenes, organotin(II) hydrides and a metalloid tin cluster are products of the studied hydrogen eliminations.…”