[{(C₅H₅)Co}₃(C₆H₅CHCHCH3)], an Organometallic Cluster with a Face‐Bridging Arene Ligand

Abstract

In contrast to the two only known complexes with μ3‐η2: η2: η2arene ligands and to benzene on densest packed metal surfaces the title complex 1 exhibits almost complete bond length equalization in the aromatic ring. 1 can be prepared in a one‐pot reaction from [CpCo(C2H4)2] and trans‐β‐methylstyrene or allylbenzene.

Organometallic benzene complexes

“…This type of bonding is not universal for all arene molecules bonded to a threefold metal site. Indeed, no alternation was observed in the carbon-carbon bond lengths of the (i3-r|6-arene complex in which a triangular array of Co atoms from a (ti5-C5H5Co)3 fragment is located above a trans-pi-methylstyrene ring (70).…”

Selective Synthesis of a Triruthenium Pentahydrido Complex with Mixed-Cp Ligands (C5tBu3H2 and C5Me5) and Its Transformation into Face-Capping Benzene Complexes: Fluxionality of a Face-Capping Benzene Ligand Induced by Oxidation

“…6 They also showed the transformation of the face-capping benzene ligand into a μ 3 -η 2benzyne ligand through irradiation 7 and migration of the benzene ligand from the μ 3 -position to the on-top position by the incorporation of an alkyne. 8 Since the first report by Lewis and Johnson, several trinuclear complexes of Ru, 9 Co, 10 Rh, 11 and Pd 12 have been synthesized, with the trinuclear planes capped by arene ligands. We reported the synthesis of [{Cp*Ru(μ-H)} 3 (μ 3 -η 2 :η 2 :η 2 -C 6 H 6 )] (2a; Cp* = η 5 -C 5 Me 5 ) by the reaction of [{Cp*Ru(μ-H)} 3 (μ 3 -H) 2 ] (1a) with 1,3-cyclohexadine 9b or benzene.…”

“…Since the first report by Lewis and Johnson, several trinuclear complexes of Ru, Co, Rh, and Pd have been synthesized, with the trinuclear planes capped by arene ligands. We reported the synthesis of [{Cp*Ru­(μ-H)} 3 (μ 3 -η 2 :η 2 :η 2 -C 6 H 6 )] ( 2a ; Cp* = η 5 -C 5 Me 5 ) by the reaction of [{Cp*Ru­(μ-H)} 3 (μ 3 -H) 2 ] ( 1a ) with 1,3-cyclohexadine or benzene .…”

Photochemische Reaktionen von Cyclopentadienylbis(ethen)rhodium mit Benzolderivaten

“…Umsetzungen von Styrolderivaten mit (im Gegensatz zu 1 bereits unter milden thermischen Bedingungen reagierendem) [CpCo(C 2 H 4 ) 2 ][19] wurden von Wadepohl und Mitarb. B. aund b-Methylstyrol, 1,1-Diphenylpropen) mit [CpCo(C 2 H 4 ) 2 ] in hohen Ausbeuten ausschlieûlich zu den jeweiligen dreikernigen l 3 -g 2 : g 2 : g 2 -Aren-Verbindungen umsetzen[21,22]. Wa Èhrend Reaktionen mit Benzol oder alkylsubstituierten Aromaten nicht zur Bildung von Co-Arenkomplexen fu È hren, lassen sich verschiedenste Styrolderivate (z.…”