A η⁴‐Dithio‐para‐benzoquinone Metal Complex

Abstract

Overcoming a long‐standing challenge: A rational synthetic procedure allows the isolation of the first stable η4‐dithio‐para‐benzoquinone complex (2; Cp*=C5Me5). The X‐ray molecular structure of 2 confirms the coordination of the elusive intermediate 1 in an η4 manner. Computational analyses of 2 support the role of the {Cp*Ir} fragment in stabilizing this reactive intermediate.

Metal-Stabilized o-Quinone Methides, Thioquinones, and Selenoquinones: Trapping Important Reactive Intermediates and Beyond

“…37 Computational analyses using DFT confirmed a net transfer of about 0.8 units of electron density to the p*-ligand lowest unoccupied molecular orbital. This additional electron density is largely localized around the thiocarbonyl bonds, resulting in a reduction in the C=S bond order as well as an anticipated decrease in the C=C bond order.…”

Supramolecular Assemblies Based on Organometallic Quinonoid Linkers: A New Class of Coordination Networks

“…[59] Pursuing our research in this area, that is, stabilization of reactive intermediates, [60,61] we discovered that {Cp*Ir} can also stabilize the elusive o-and p-dithiobenzoquinone intermediates. [25] Our synthetic approach is completely different from that reported for the quinone methide. It involves the synthesis of halogenated 1, (9), which are the key molecules for 2 d and 2 e. Subsequent substitution of the chlorides by HS À provided the target compounds 2 d and 2 e in high yields (Scheme 8).…”

“…In only a few examples was a metalated bridging ligand used. [19][20][21] In contrast, we have recently found that our rhodium and iridium p-benzoquinone complexes [Cp*M(p-benzoquinone)] (M = Rh, L Rh ; M = Ir, L Ir ) are stable, easy to prepare, and adequate organometallic bridging ligands [22][23][24][25] to construct a novel family of supramolecular assemblies (Figure 1).…”

Supramolekulare Aggregate mit metallorganischen Chinon‐Linkern: eine neue Klasse von Koordinationsnetzwerken

“…[59] Im Zuge unserer Forschungen über die Stabilisierung reaktiver Intermediate [60,61] stellten wir fest, dass {Cp*Ir} auch die kurzlebigen o-und p-Dithiobenzochinon-Intermediate stabilisieren kann. [25] Unsere Synthesemethode umfasst die …”

“…Rh ; Ir, L Ir ) stabil sind, einfach hergestellt werden können und geeignete metallorganische Linker [22][23][24][25] zum Aufbau supramolekularer Strukturen ergeben (Abbildung 1).…”