Linear, mixed-valent homocatenated tri-tin complexes featuring Sn–Sn bonds

Abstract

Reduction of LPhSnCl with 0.66 eq. of LiBsBu3H affords the mixed-valent homocatenated tri-tin complex (LPhSn)3Cl whose HOMO primarily comprises σ-bonding along the Sn–Sn–Sn framework.

Controlling Catenation in Germanium(I) Chemistry through Hemilability

“…From ab roader perspective,t he formation of ac hain of four Ge I atoms in 2 is highly unusual and represents av ery rare example of linear catenation among the heavier Group 14 compounds-particularly because it involves metal-metal bonds which are not additionally supported by ab ridging ligand. [26][27][28]35] Simple catenation is typically disfavoured due to entropic factors and the increasingly weak nature of the E-E bonds upon descending the group.With this in mind, we were keen to explore how aggregation of this type might be controlled. Conceivably, 2 arises through transient Scheme 3.…”

“…Recently, a series of linear, mixed‐valent homo‐catenated tri‐tin complexes (L Ph Sn) 3 X ( VI , L Ph =2,5‐di( o ‐pyridyl)‐3,4‐diphenylpyrrolate; X=Cl, AlCl 4 , OTf, PF 6 ) which feature unsupported Sn‐Sn‐Sn linkages were reported by Liu et al. [27] Within the realm of Ge I chemistry, 2,6‐diamidopyridyl ligands have been employed to isolate a catenated octagermylene(I) complex ( VII ). [28] However, this cyclic system features Ge−Ge bonds which are supported by a bridging ligand scaffold, and, to the best of our knowledge, examples of linear metal‐metal bonded chains of Ge I monomers are not known (for >2 metal atoms).…”

“…[26] While anumber of landmark cyclic/polycyclic systems of this composition have been reported, [26] linear chain homo-catenated systems akin to poly-or oligo-acetylenes featuring alternating double and single bonds (i.e.o ligo-dimetallynes) are unprecedented. Recently,aseries of linear, mixed-valent homo-catenated tri-tin complexes (L Ph Sn) 3 X( VI,L Ph = 2,5-di(o-pyridyl)-3,4diphenylpyrrolate;X = Cl, AlCl 4 ,O Tf,P F 6 )w hich feature unsupported Sn-Sn-Sn linkages were reported by Liu et al [27] Within the realm of Ge I chemistry,2,6-diamidopyridyl ligands have been employed to isolate ac atenated octagermylene(I) complex (VII). [28] However,t his cyclic system features Ge À Ge bonds which are supported by ab ridging ligand scaffold, and, to the best of our knowledge,e xamples of linear metalmetal bonded chains of Ge I monomers are not known (for > 2 metal atoms).…”

Controlling Catenation in Germanium(I) Chemistry through Hemilability

“…From a broader perspective, the formation of a chain of four Ge I atoms in 2 is highly unusual and represents a very rare example of linear catenation among the heavier Group 14 compounds—particularly because it involves metal‐metal bonds which are not additionally supported by a bridging ligand [26–28, 35] . Simple catenation is typically disfavoured due to entropic factors and the increasingly weak nature of the E‐E bonds upon descending the group.…”

“…oligo‐dimetallynes) are unprecedented. Recently, a series of linear, mixed‐valent homo‐catenated tri‐tin complexes (L Ph Sn) 3 X ( VI , L Ph =2,5‐di( o ‐pyridyl)‐3,4‐diphenylpyrrolate; X=Cl, AlCl 4 , OTf, PF 6 ) which feature unsupported Sn‐Sn‐Sn linkages were reported by Liu et al [27] . Within the realm of Ge I chemistry, 2,6‐diamidopyridyl ligands have been employed to isolate a catenated octagermylene(I) complex ( VII ) [28] .…”