Perstannylated Ammonium and Phosphonium Ions: Organometallic Onium Ions That Are also Base-Stabilized Stannylium Ions

Drieß, Matthias; Monsé, Christian; Merz, Klaus; Wüllen, Christoph van

doi:10.1002/1521-3773(20001016)39:20<3684::aid-anie3684>3.0.co;2-u

Cited by 17 publications

(1 citation statement)

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“…Section , Addendum]. Bridging phosphide ligands are relatively common among main group metals as compared to their carbide counterparts, which are almost exclusively confined to transition metals. − There are even stable thorium and uranium coordination complexes bearing bridging phosphide ligands, at variance with carbide. As for preparative strategies, many phosphide complexes derive from P 4 (three-electron reduction of 1/4 equivalent), ,,,− whereas elemental carbon very rarely is a precursor for carbide complexes (Figure , Figure ).…”

Section: Strategies Toward Bridging Carbide Complexesmentioning

confidence: 99%

Transition Metal Carbide Complexes

Reinholdt

Bendix

2021

Chem. Rev.

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Carbide complexes remain a rare class of molecules. Their paucity does not reflect exceptional instability but is rather due to the generally narrow scope of synthetic procedures for constructing carbide complexes. The preparation of carbide complexes typically revolves around generating L n M−CE x fragments, followed by cleavage of the C−E bonds of the coordinated carbon-based ligands (the alternative being direct C atom transfer). Prime examples involve deoxygenation of carbonyl ligands and deprotonation of methyl ligands, but several other p-block fragments can be cleaved off to afford carbide ligands. This Review outlines synthetic strategies toward terminal carbide complexes, bridging carbide complexes, as well as carbide−carbonyl cluster complexes. It then surveys the reactivity of carbide complexes, covering stoichiometric reactions where the carbide ligands act as C 1 reagents, engage in cross-coupling reactions, and enact Fischer−Tropsch-like chemistry; in addition, we discuss carbide complexes in the context of catalysis. Finally, we examine spectroscopic features of carbide complexes, which helps to establish the presence of the carbide functionality and address its electronic structure.

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Section: Strategies Toward Bridging Carbide Complexesmentioning

confidence: 99%

Transition Metal Carbide Complexes

Reinholdt

Bendix

2021

Chem. Rev.

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E(SiMe3)4+ (E=P, As): persilylierte Phosphonium- und Arsoniumionen

et al. 2001

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Erst stark Lewis‐acide, arensolvatisierte Me3Si+‐Ionen reagieren mit E(SiMe3)3‐Verbindungen (E=P, As) zu den kristallographisch gesicherten E(SiMe3)4+‐Oniumionen 1 (siehe linkes Bild), die stark negativ polarisierte P‐ bzw. As‐Atome enthalten. Die maskierten Me3Si+‐Ionen in 1 können leicht auf Et2O übertragen werden, wobei das erstmals auch strukturell charakterisierte, planare Silyloxoniumion [Et2(Me3Si)O]+ 2 (rechtes Bild) entsteht.

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