New Monocyclopentadienyl Complexes of Tantalum(V) and Titanium(IV) with Chelating Pyrimidinethiolate and Oxypyridine Ligands − Molecular Structure of [Cp*TaCl3(SC6H7N2)]
✍ Scribed by Rosa Fandos; Carolina Hernández; Antonio Otero; Ana Rodríguez; María José Ruiz; Pilar Terreros
- Publisher
- John Wiley and Sons
- Year
- 2003
- Tongue
- English
- Weight
- 135 KB
- Volume
- 2003
- Category
- Article
- ISSN
- 1434-1948
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✦ Synopsis
Abstract
New monocyclopentadienyl species of Ta^V^, [Cp*TaL~3~(XR)] (L = Cl, Me, X = O, S) bearing 4,6‐dimethyl‐2‐pyrimidinethiolate (SR = SC~6~H~7~N~2~) or 3‐cyano‐4,6‐dimethyloxypyridine (OR = OC~8~H~7~N~2~) ligands were prepared, namely [Cp*TaCl~3~(SC~6~H~7~N~2~)] (1), [Cp*TaCl~3~(OC~8~H~7~N~2~)] (2), [Cp*TaMe~3~(SC~6~H~7~N~2~)] (3). In addition, a bis(oxypyridine)titanium(IV) complex [Cp*TiMe~2~(OC~8~H~7~N~2~)~2~] was isolated. The X‐ray structure analysis of 1 revealed that the thiolate group is bonded to the metal center through the sulfur atom and one of the nitrogen atoms in an η^2^‐fashion. The reactivity of complex 3 with isocyanides (CNR), R = __t__Bu, Xyl (Xyl = 2,6‐dimethylphenyl) was also studied showing differences depending on the nature of R group. The reaction with 2,6‐dimethylphenyl isocyanide gives the azatantalacyclobutane complex [Cp*TaMe{XylN=CC(Me~2~)NXyl}(SC~6~H~7~N~2~)] (5) as the final product, whereas in the reaction with tert‐butyl isocyanide the η^2^‐imine‐containing complex [Cp*Ta{__t__BuNC(Me~2~)}(SC~6~H~7~N~2~)] (6) is proposed to be formed. The dynamic behavior of [Cp*TaMe~3~(SC~6~H~7~N~2~)] (3) was also studied by variable‐temperature ^1^H NMR spectroscopy. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)