A Tripodal Triaminostannate as a Metal Nucleophile: Synthesis of Transition Metal−Tin Heterodimetallic Complexes

Abstract

The coordination capability of the previously reported triamidostannate [MeSi{SiMe2N(4‐CH3C6H4)}3SnLi(OEt2)] (1) as a precursor for transition metal−tin heterodimetallic complexes is presented. Whereas reaction with CH3I, Me3SiCl, or Me3SnCl yielded the derivatives [MeSi{SiMe2N(4‐CH3C6H4)}3Sn−R] (R = Me, 2; Me3Si, 3; Me3Sn, 4), demonstrating the nucleophilic properties of the stannate(II), its complexation to transition metal centres was achieved by halide substitution with [CuCl(PPh3)]4, [CpM(CO)2X] (M = Fe, X = Cl; M = Ru, X = Br), [CpM(CO)3Cl] (M = Mo, W) and trans(Cl)‐[RuCl2(bpy)(CO)2] to give [MeSi{SiMe2N(4‐CH3C6H4)}3Sn−Cu(PPh3)] (5), [MeSi{SiMe2N(4‐CH3C6H4)}3Sn− M(CO)2Cp (M = Fe: 6; Ru: 7)], [MeSi{SiMe2N(4‐CH3C6H4)}3Sn−M(CO)2Cp] (M = Mo: 8; W: 9) and [(MeSi{SiMe2N(4‐CH3C6H4)}3Sn)2Ru(bpy)(CO)2] (10), of which 6, 9 and 10 were characterized by X‐ray diffraction.

Diaminogermylene and Diaminostannylene Derivatives of Gold(I): Novel AuM and AuM2(M = Ge, Sn) Complexes

“…Concerning anionic group 14 di- or triaminometalate ligands in group 11 metal complexes, a few examples are known for the three transition metals. They all have been prepared by either inserting a diaminometalene into an Au–Cl bond (compound G in Figure ) or displacing one (compound H in Figure ) − or two (compounds I and J in Figure ) anionic ligands from the appropriate transition-metal precursor with a group 14 triaminometalate reagent. Similar substitution reactions have also allowed the preparation of some gold­(II) and gold­(III) complexes, not depicted in Figure , that contain the triaminostannate ligand of H and I …”

Tripodal Triamidometallates of the Heavy Group 14 Elements: Inorganic Cages with Remarkable “Ligand Properties”

“…[36] Several examples of such late transition metal tin complexes, all obtained by salt metathesis of a stannate with the respective chloro or bromo complexes, are summarized in Scheme 7. [37] Scheme 7. Coordination of a tripodal triamidostannate to late transition metal complex fragments…”

“…[38] We were able to provide the first crystallographically characterized example of a digermanylaurate (26) (PPh 3 )] (28) [37] and [MeSi{SiMe 2 N(4-CH 3 C 6 H 4 )} 3 -SnϪAu(PPh 3 )] (29) (Scheme 9). [40] The formation of SnϪCu and SnϪAu bonds in these complexes is supported by the observation of 117/119 Sn satellites in their 31 P NMR spectra.…”

Syntheses and Structural Characterization of the Heavier Alkali-Metal Stannates Bearing the Tripodal Triamino Framework: Structural Trends in the Series of [MeSi{SiMe2N(4-CH3C6H4)}3Sn][M] (M = Na, K, Rb)

“…We recently began to study the structural details of anionic tripodal triaminostannates(II) and their use as “ligands” in transition-metal chemistry. − In this paper, we report the synthesis and structural characterization of a novel trisilylsilane-derived hexaaminodistannane and its conversion by reductive cleavage to the corresponding heavier alkali-metal (sodium, potassium, rubidium) stannates(II). This allowed us to conduct a systematic, comparative structural study of the interactions between the group 1 cations and the stannate cages.…”