The CC coupling of aryl nitriles at Group 4 metallocenes leads to unusual ring-strained 1-metalla-2,5-diaza-cyclopenta-2,4-dienes. The structural, energetic, and chemical properties of these complexes are described. The reactions of these compounds towards CH3 CN, H2 , CO2 , and HCl usually lead to the release of one nitrile and its replacement by different co-substrates.

Reactions of Group 4 metallocene alkyne complexes [Cp'2M(η(2)-Me3SiC2SiMe3)] (1: M = Zr, Cp' = Cp* = η(5)-pentamethylcyclopentadienyl; 2 a: M = Ti, Cp' = Cp*, and 2 b: M = Ti, Cp'2 = rac-(ebthi) = rac-1,2-ethylene-1,1'-bis(η(5)-tetrahydroindenyl)) with diphenylacetonitrile (Ph2CHCN) and of the seven-membered zirconacyclocumulene 3 with phenylacetonitrile (PhCH2CN) were investigated. Different compounds were obtained depending on the metal, the cyclopentadienyl ligand and the reaction temperature. In the first step, Ph2CHCN coordinated to 1 to form [Cp*2Zr(η(2)-Me3SiC2SiMe3)(NCCHPh2)] (4). Higher temperatures led to elimination of the alkyne, coordination of a second Ph2CHCN and transformation of the nitriles to a keteniminate and an imine ligand in [Cp*2Zr(NC2Ph2)(NCHCHPh2)] (5). The conversion of 4 to 5 was monitored by using (1)H NMR spectroscopy. The analogue titanocene complex 2 a eliminated the alkyne first, which led directly to [Cp*2Ti(NC2Ph2)2] (6) with two keteniminate ligands. In contrast, the reaction of 2 b with diphenylacetonitrile involved a formal coupling of the nitriles to obtain the unusual four-membered titanacycle 7. An unexpected six-membered fused zirconaheterocycle (8) resulted from the reaction of 3 with PhCH2CN. The molecular structures of complexes 4, 5, 6, 7 and 8 were determined by X-ray crystallography.

The reactions of [Cp*2 Ti(η(2) -Me3 SiC2 SiMe3 )] (Cp*=η(5) -pentamethylcyclopentadienyl) with various dicyano compounds were investigated. Nitrile-nitrile CC couplings result in multinuclear complexes owing to the bifunctionality of the substrates. Applying 1,3- or 1,4-dicyanobenzene led to tri- and tetranuclear complexes of the rare 1-metalla-2,5-diaza-cyclopenta-2,4-dienes. These are potential catalysts and were tested in the ring-opening polymerization of ε-caprolactone. The reaction with adiponitrile as alkyl dinitrile afforded a trinuclear 1-metalla-2,5-diaza-cyclopent-3-ene through additional protonation of the nitrogen atoms. The structure and bonding of the products were investigated by X-ray crystallography and DFT analysis to understand the molecular organization in the macrocycles.

Abstract:The reactions of the group 4 metallocene alkyne complexes Cp* 2 M(η 2 -Me 3 SiC 2 SiMe 3 ) (M = Ti, Zr) with different cyanopyridines were investigated. For the zirconium compound, the unstable products Cp* 2 Zr(η 2 -Me 3 SiC 2 SiMe 3 )(N≡C-py) were first formed by the end-on coordination of the substrate. Subsequent reaction with a second equivalent resulted in the elimination of the alkyne and in the formation of 1-zircona-2,5-diazacyclopenta-2,4-dienes. By applying (2-bromo)-5-cyanopyr-

The reactions of the seven-membered zirconacyclocumulene [Cp 2 Zr{η 4 -Me 3 SiC 4 (SiMe 3 )-C(C 2 SiMe 3 )=CSiMe 3 }] (1) with nitriles (RCϵN, R = Me, Ph) started with an insertion of a cyanide group into the metal-butadiyne bond followed by an alkyne-nitrile coupling and formation of 1-zircona-2-azacyclopenta-2,4-dienes. The reaction product for R = Me is stabilized by dimerization to give a compound containing a four-membered -N-Zr-N-Zr-ring and two identical fivemembered 1-metalla-2-aza-cyclopentadiene rings. In case of R = Ph, a metallacycle could not be isolated, and a pyrimidine[a] Leibniz-5304 was formed. The catalytic potential of this reaction was investigated. For PhN=C(H)Ph, again after insertion and coupling, a corresponding 1-zircona-2-azacyclopenta-4-ene was established. The reaction of this compound with carbon dioxide led to ring expansion and formation of a seven-membered product, which released CO 2 at higher temperature and to give back the reactant. The above-mentioned products were characterized by NMR spectroscopy and singlecrystal X-ray structure analysis.ing from these alkyne complexes, five-membered, all-carbon metallacycles, such as 1-metallacyclopenta-2,4-dienes (metallacyclopentadienes A, Scheme 1), 1-metallacyclopent-3-ynes (metallacyclopentynes B, Scheme 1), and 1metallacyclopenta-2,3,4-trienes (metallacyclocumulenes C, Scheme 1), were synthesized to study their reaction behavior. [2,3] In many cases, coupling reactions of two alkynes were observed to yield 1-metallacyclopenta-2,4-dienes A. [5] We were now interested in the formation of the analogous heterocycles by the coupling of nitriles. The corresponding 1-metalla-2,5-diazacyclopenta-2,4-dienes D (Scheme 1), which result from a nitrile-nitrile coupling, are very rare. [6] Lately, these metallacycles were synthesized by reaction of arylnitriles with [Cp* 2 M(η 2 -Me 3 SiC 2 SiMe 3 )] (M = Ti, Zr; Cp* = η 5 -pentamethylcyclopentadienyl). [7] Additionally, there were hints for the formation of the corresponding five-membered 1-metalla-2-aza-cyclopenta-2,4-dienes E (Scheme 1), established by an alkyne-nitrile C-C coupling, which were assumed as intermediates in the synthesis of heteroaromatic compounds. [8] To the best of our knowledge, only in the case of 3-ferrocenyl-2-propyne-nitrile and zirconocene [7b] and for an aluminum complex [6a] has the corresponding metallacyclopentadiene E been isolated by alkyne-nitrile coupling.

The reactions of the Group 4 metallocene alkyne complexes, [Cp*2M(η2-Me3SiC2SiMe3)] (1 a: M=Ti, 1 b: M=Zr, Cp*=η5-pentamethylcyclopentadienyl), with the ferrocenyl nitriles, Fc-CN and Fc-C≡C-C≡N (Fc=Fe(η5-C5H5)(η5-C5H4)), is described. In case of Fc-C≡N an unusual nitrile–nitrile C-C homocoupling was observed and 1-metalla-2,5-diaza-cyclopenta-2,4-dienes (3 a, b) were obtained. As the first step of the reaction with 1 b, the nitrile was coordinated to give [Cp*2Zr(η2-Me3SiC2SiMe3)(N≡C-Fc)] (2 b). The reactions with the 3-ferrocenyl-2-propyne-nitrile FcC≡C-C≡N lead to an alkyne–nitrile C-C coupling of two substrates and the formation of 1-metalla-2-aza-cyclopenta-2,4-dienes (4 a, b). For M=Zr, the compound is stabilized by dimerization as evidenced by single-crystal X-ray structure analysis. The electrochemical behavior of 3 a, b and 4 a, b was investigated, showing decomposition after oxidation, leading to different redox-active products.

In this work the reactivity of 1-metalla-2,5-diaza-cyclopenta-2,4-dienes of group 4 metallocenes, especially of the pyridyl-substituted examples, towards small molecules is investigated. The addition of H2 , CO2 , Ph-C≡N, 2-py-C≡N, 1,3-dicyanobenzene or 2,6-dicyanopyridine results in exchange reactions, which are accompanied by the elimination of a nitrile. For CO2 , a coordination to the five-membered cycle occurs in case of Cp*2 Zr(N=C(2-py)-C(2-py)=N). A 1,4-diaza-buta-1,3-diene complex is formed by H-transfer in the conversion of the analogous titanocene compound with CH3 -C≡N, PhCH2 -C≡N or acetone. For CH3 -C≡N a coupling product of three acetonitrile molecules is established additionally. In order to split off the metallocene from the coupled nitriles, we examined reactions with HCl, PhPCl2 , PhPSCl2 and SOCl2 . In the last case, the respective thiadiazole oxides and the metallocene dichlorides were obtained. A subsequent reaction produced thiadiazoles.

Reactions of the group 4 metallocene alkyne complexes [Cp'2 M(η(2) -Me3 SiC2 SiMe3 )] [Cp'2 =rac-(ebthi)=rac-1,2-ethylene-1,1'-bis(η(5) -tetrahydroindenyl): M=Ti, Zr, Hf; Cp'2 =Cp*2 (Cp*=η(5) -pentamethylcyclopentadienyl): M=Zr] with 2,6-dimethylphenyl isocyanide (2-xylyl isonitrile, XyNC) were investigated. Depending on the metal, the Cp' ligand, and/or the stoichiometry, as well as the reaction temperature and time, different products were obtained. The products included simple end-on coordination compounds of XyNC in addition to those of the coupling of Me3 SiC2 SiMe3 with two, three, or four isonitriles to form enimine complexes, aza-metallacycloallenes, and fused heterocyclic systems, respectively. One example of the latter tricyclic compounds was subject to demetalation by using HCl. Molecular structures of the heterometallacycles were determined by X-ray crystallography. The interconversion of the products was investigated by (1) H NMR spectroscopy.