Synthesis and Molecular Structure of a Hexaaminodistannane Comprising two Identical Triaminotin Subunits

Abstract

Reaction of the previously characterized lithium stannate [HC{SiMe2N(4‐CH3C6H4)}3SnLi(thf)3] (1) with AgCl afforded the corresponding distannane [HC{SiMe2N(4‐CH3C6H4)}3Sn]2 (2) as the product of an oxidative coupling in good yield. Its [2, 2, 2]bicyclooctane‐related cage structure, comprising the trisilylmethane unit and the triamido‐tin fragment, as well as the Sn‐Sn bond (2.8204(4)Å) were established by single crystal structure analysis: Space group group P21/n, Z = 2, lattice dimensions at 120(2) K: a = 13.6515(3), b = 15.8391(3), c = 16.3522(3)Å, β = 102.7760(10)°, R1 = 0.0347.

6 Carbon, silicon, germanium, tin and lead

“…Studies into the nucleophilic character of triaminostannates has given rise to the first crystallographically characterised hexaamidodistannane with identical tripodal triamine ligands 11. 33 The Sn-Sn bond length (2.820 A ˚) is consistent with other known examples. More striking, however, is the unusual and deeply impressive nonaphenyl tetraplumbate(IV) 12 isolated as its bromomagnesium salt from the deceptively simple reaction shown.…”

Reactivity of Bis(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopent-1-yl)tin with CO2, OCS, and CS2 and Comparison to That of Bis[bis(trimethylsilyl)amido]tin

“…The Sn−Sn bond length of Gade’s distannane measured 2.8204(4) Å, in very good agreement with 5 . The Sn−N bond lengths for Sn(1)−N(1) and Sn(2)−N(12) are noticeably shorter [2.021(2)−2.025(3) Å] than those of Sn(3)−N(31) and Sn(3)−N(32) at 2.089(3) Å, consistent with the higher formal oxidation state of Sn(1) and Sn(2) . The N−Sn−N bond angles around Sn(1) and Sn(2) are larger, measuring 111.44(10) and 109.89(11)°, respectively, while the N−Sn−N bond angle for Sn(3) is 99.81(10)°.…”

Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S3˙−

“…While more work is required to substantiate this proposal, such a postulated neutral [Sn 2 ( m BDCA-5t)] species may exist as a Sn–Sn bonded hexaaminodistannane analogous to one which Gade et al obtained upon oxidative coupling of a tin( ii ) triamidostannate and for which the Sn–Sn interatomic distance was reported to be 2.8204(4) Å. 38 The metal–metal single bond in such a species corresponds to the HOMO–1 of complex 1 ( Fig. 2b ).…”