Treatment of the mu3-ethylidyne complex [{TiCp*(mu-O)}3(mu3-CMe)](1), (Cp*=eta5-C5Me5) with alkali metal amides leads to the oxoheterometallocubane derivatives [M(mu3-O)3{(TiCp*)3(mu3-CCH2)}] [M = Li (2), Na (3), K (4), Rb (5), Cs (6)] containing the naked carbanion mu3-CCH2-; the addition of triphenylmethanol and tert-butanol to the compounds 2-6 gives rise to the oxoderivatives [{TiCp*(mu-O)}3(mu-CHMe)(OCR3)][R = Me (7), Ph (8)] which show a mu-ethylidene bridge on the surface model Ti3O3.

Deprotonierung des Komplexes [{Ti(η5‐C5Me5)(μ‐O)}3(μ3‐CH)] mit Alkalimetallalkylen und ‐amiden erwies sich als zuverlässige Methode zur Intercalierung von Alkalimetallionen zwischen metallorganische Titanoxidschichten (siehe Bild). Der Intercalierungsprozess und die erhaltenen Strukturen wurden anhand von DFT‐Rechnungen analysiert.

Deprotonation of the complex [{Ti(η5‐C5Me5)(μ‐O)}3(μ3‐CH)] with different alkali metal alkyl and amide reagents provides a method for the intercalation of alkali‐metal ions into layered organometallic titanium oxides (see picture). The process and the structures were analyzed by DFT calculations.

The μ3‐methylidyne group of the complex [{TiCp*(µ‐O)}3(µ3‐CH)] (1) (Cp* = η5‐C5Me5) was deprotonated by amides of the group 1 elements, [MN(SiMe3)2] (M = Li, Na, K, Rb, Cs) to form the oxoheterometallocubane complexes [M(μ3‐O)3{Ti3Cp*3(μ3‐C)}] [M = Li (3), Na (4), K (5), Rb (6), Cs (7)]. Similar treatments of 1 with the alkaline‐earth amides [M{N(SiMe3)2}2(thf)2] (M = Mg, Ca, Sr) afforded the heterometallocubane derivatives [{(thf)x(Me3Si)2NM}(μ3‐O)3{Ti3Cp*3(μ3‐C)}] [M = Mg, x = 0, (8); Ca, x = 1, (9); Sr, x = 1, (10)] in high yields. The addition of ligands such as cyclopentadiene (C5H6) or pentamethylcyclopentadiene (C5Me5H) to the compounds 3−7 allowed recovery of the μ3‐methylidyne oxocomplex 1. The analogous reaction of 8−10 with C5H6 caused the displacement of the amide fragment to give the heterometallocubanes [(CpM)(μ3‐O)3{Ti3Cp*3(μ3‐C)}] [M = Mg (11), Ca (12), Sr (13)], while C5Me5H reacts only with 9 and 10 to give the compounds [(Cp*M)(μ3‐O)3{Ti3Cp*3(μ3‐C)}] [M = Ca (14), Sr (15)]. Furthermore, heating of the species 8−10 in the presence of the starting complex 1 produced amine elimination and afforded the corner‐shared heterometallodicubanes [M{(μ3‐O)3Ti3Cp*3(μ3‐C)}2] [M = Mg (16), Ca (17), Sr (18)]. Treatment of 1 with the amide [Ba{N(SiMe3)2}2(thf)2] or dialkyl derivatives of magnesium [MgR2(thf)2] (R = CH2Ph, tBu) and barium [Ba(CH2Ph)2] provided the corner‐shared metallodicubanes [M{(μ3‐O)3Ti3Cp*3(μ3‐C)}2] [M = Mg(16), Ba(19)]. The molecular structures of complexes 9, 16, 17 and 18 have been established by single‐crystal X‐ray analyses. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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