Preparation and Molecular Structure of a Cationic Bisplumbylene

Abstract

A cationic phosphanyl substituted plumbylene has been generated by chloride abstraction from a neutral bisplumbylene embedded into a bicyclic [3]ferrocenophane scaffold. The primary cationic bisplumbylene [Fe(C 5 H 4 PtBuPb) 2 Cl] + -AlCl 4 has been characterized by multinuclear NMR spectroscopy, mass spectrometry, and elemental analysis. It undergoes rapid chloride exchange with its neutral counterpart in solution, [a]

Bending Ferrocenes with Low Coordinated Bridging Units: The Investigation of Carbenes and Their Analogues with a Ferrocenophane Backbone

“…Recently, also diaminocarbene[3]­ferrocenophanes (Scheme , VIII ) were synthesized as stable entities. − Unlike most of the NHCs, − these species were able to activate small molecules such as CO or NH 3 . Besides carbene VIII , the syntheses of several heavier congeners such as silylenes ( IX ), germylenes ( X ), − stannylenes ( XI ), , and plumbylenes ( XII ) , were reported as well.…”

“…41−44 Unlike most of the NHCs, 1−18 these species were able to activate small molecules such as CO or NH 3 . 21 Besides carbene VIII, the syntheses of several heavier congeners such as silylenes (IX), 45 germylenes (X), 46−48 stannylenes (XI), 46,48 and plumbylenes (XII) 49,50 were reported as well.…”

A Ferrocenophane-Based Diaminophosphenium Ion

“…A class of cyclic diaminocarbenes and diaminocarbene homologues that has recently gathered attention are ferrocenophane-based tetrylenes IVb – e , − in which the five-membered heterocyclic ring is formally replaced by a [3]­ferrocenophane backbone . The combination of the subvalent main-group element with a redox-active ferrocene unit provides for an interesting chemistry that enabled, among others, the generation of unprecedented persistent tetrylene radical cations. , The cationic carbene derivatives feature a peculiar delocalization of the spin density between the ferrocene unit and the subvalent carbon atom, while their heavier homologues exhibit a localized ferrocenium-type nature which does not compromise the tetrylene character .…”

At the limits of bisphosphonio‐substituted stannylenes

“…In contrast to its stannylene analog 6 a, plumbylene 7 stabilizes by intermolecular dimerization via μ-Cl bridges, similar to other lead chlorides. [19,26] Symmetric contacts are found between Pb1 and both phosphorus atoms with bond lengths of Pb1-P1 2.935(2) Å and Pb1-P2 2.915(3) Å. Literature known low coordinate lead(II) complexes show PbÀ P bond lengths between 2.715(5) Å and 2.971(5) Å.…”