1-Zirconacyclobuta-2,3-dienes: synthesis of organometallic analogs of elusive 1,2-cyclobutadiene, unprecedented intramolecular C-H activation, and reactivity studies.

The structure, bonding, and reactivity of small, highly unsaturated ring systems is of fundamental interest for inorganic and organic chemistry. Four-membered metallacyclobuta-2,3-dienes, also referred to as metallacycloallenes, are among the most exotic examples for ring systems as these represent organometallic analogs of 1,2-cyclobutadiene, the smallest cyclic allene. Herein, the synthesis of the first examples of 1-zirconacyclobuta-2,3-dienes of the type [Cp'2Zr(Me3SiC3SiMe3)] (Cp'2 = rac-(ebthi), (ebthi = 1,2-ethylene-1,1'-bis(η5-tetrahydroindenyl)) (2a); rac-Me2Si(thi)2, thi = (η5-tetrahydroindenyl), (2b)) is presented. Both complexes undergo selective thermal C-H activation at the 7-position of the ansa-cyclopentadienyl ligand to produce a new type of "tucked-in" zirconocene system, 3a and 3b, that possesses a η3-propargyl/allenyl ligand. Both types of complexes react with carbonyl compounds, producing enynes in the case of 2a and 2b, as well as η1-allenyl complexes for 3a and 3b. Computational analysis of the structure and bonding of 2a and 3a reveals significant differences to a previously described related Ti complex. All complexes were fully characterised, including X-ray crystallography and experimental results were supported by DFT analysis.

Synthesis of novel carbohydrate based pyridinium ionic liquids and cytotoxicity of ionic liquids for mammalian cells.

The large pool of naturally occurring carbohydrates with their diversity in chirality and structure led to the idea of a systematic investigation of carbohydrate based ILs. To this end, we investigated the influence of different ether groups, mainly methyl or ethyl ether, on the secondary OH groups as well as different configurations on physical properties such as melting point, thermostability and especially the influence on cell toxicity. For this investigation we chose α- and ß-methyl-, ß-allyl- and ß-phenyl d-glucopyranose as well as four 1-deoxy-pentoses. In order to be able to classify the results, more ionic liquids with different structural motives were examined for cytotoxicity. Here, we present data that confirm the biocompatibility of such ILs consisting of naturally occurring molecules or their derivatives. The synthesized carbohydrate based ILs were tested for their suitability as additives in coatings for medical applications such as drug-eluting balloons.

A general benzylic C-H activation and C-C coupling reaction of zirconocenes mediated by C-N bond cleavage in tert-butylisocyanide - unusual formation of iminoacyl complexes.

Reactions of the zirconocene alkyne complex [rac-(ebthi)Zr(η2-Me3SiC2SiMe3)] (rac-(ebthi) = rac-1,2-ethylene-1,1'-bis(η5-tetrahydroindenyl)) with tert-butylisocyanide and methylbenzenes were investigated. Depending on the stoichiometry, the solvent and the reaction temperature different products were obtained. Starting with the end-on coordination of the isocyanide to the zirconium centre (2), elevated reaction temperatures and an excess of tert-butylisocyanide resulted after the elimination of the alkyne in the formation of zirconocene η2-iminoacyl cyanide complexes 3a-d. These complexes are formed by coupling with a benzyl fragment through C-H bond activation of a methyl group of methylbenzene. The dimeric cyanide bridged zirconocene complex 4 is formed as a side-product of this process. The unexpected dimer and the heterometallacycles were fully characterised, including X-ray crystallography.

1-Titanacyclobuta-2,3-diene - an elusive four-membered cyclic allene.

The synthesis of an unusual 1-metalla-2,3-cyclobutadiene complex [rac-(ebthi)Ti(Me3SiC3SiMe3)] (rac-ebthi = rac-1,2-ethylene-1,1'-bis(η5-tetrahydroindenyl)), a formal metallacyclic analogue of a non-existent four-membered 1,2-cyclobutadiene, is described. By variation of the cyclopentadienyl ligand of the titanocene precursor it was possible to stabilise this highly exotic compound which selectively reacts with ketones and aldehydes to yield enynes by oxygen transfer to titanium. Analysis of the bonding and electronic structure of the metallacycle shows that the complex is best described as an unusual antiferromagnetically coupled biradicaloid system, possessing a formal Ti(iii) centre coordinated with a monoanionic radical ligand.

Visiting the Limits between a Highly Strained 1-Zirconacyclobuta-2,3-diene and Chemically Robust Dizirconacyclooctatetraene.

The reaction of the allene precursor Li2 (Me3 SiC3 SiMe3 ) with [Cp2 ZrCl2 ] (Cp=cyclopentadienyl) was examined. The selective formation of hitherto unknown linear, allene-bridged dizirconocene complexes [(Cp2 ZrCl)2 {-µ-(Me3 Si)C3 (SiMe3 )-}] and [(Cp2 Zr)2 {-µ-(Me3 Si)C3 (SiMe3 )-}2 ] was observed. Upon σ coordination of the allenediyl unit to {Cp2 Zr}, pyrophoric Li2 (Me3 SiC3 SiMe3 ) is tamed stepwise to yield a surprisingly robust 1,5-dizirconacyclooctatetra-2,3,6,7-ene with cumulated double bonds. This complex is unexpectedly inert against moisture, air, water and acetone. Surprisingly, it degrades under MS conditions to give the highly strained 1-zirconacyclobuta-2,3-diene. All compounds isolated have been fully characterised and the molecular structures are discussed. The stability and reactivity of these complexes are rationalised by DFT computations.

Titanocene Silylpropyne Complexes: Promising Intermediates en route to a Four-Membered 1-Metallacyclobuta-2,3-diene?

Coordination of the alkyl-substituted alkynes Me3 SiC2 CH2 R (1: R=SiMe3 ; 2: R=N(SiMe3 )2 ) to titanocene centres [Cp'2 Ti] (Cp'=Cp, Cp*) yields stable alkyne complexes of the type Cp'2 Ti(η2 -Me3 SiC2 CH2 R) (3: Cp'=Cp, R=SiMe3 ; 5: Cp'=Cp, R=N(SiMe3 )2 ; 6: Cp'=Cp*, R=SiMe3 ) that are not prone to alkyne/allene isomerisation. When reacting alkyne 2 with Cp*2 TiCl2 and Mg formation of the complex Cp*2 Ti(III)(η3 -Me3 SiC2 CH2 ) (7) which displays a propargylic unit coordinated to the TiIII centre takes place. All complexes were fully characterised, the molecular structures for 5, 6, and 7 are discussed.