NDLI: Ring Opening and Bidentate Coordination of Amidinate Germylenes and Silylenes on Carbonyl Dicobalt Complexes: The Importance of a Slight Difference in Ligand Volume

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Ring Opening and Bidentate Coordination of Amidinate Germylenes and Silylenes on Carbonyl Dicobalt Complexes: The Importance of a Slight Difference in Ligand Volume

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Cabeza, Javier A. García-álvarez, Pablo Pérez-carreño, Enrique Polo, Diego
Description	Author Affiliation: Cabeza JA ( Departamento de Química Orgánica e Inorgánica-IUQOEM, Universidad de Oviedo-CSIC, E-33071 Oviedo (Spain), Fax: (+34) 985103446. jac@uniov.es.)
Abstract	The reactions of $[Co_{2}(CO)_{8}]$ with one equiv of the benzamidinate $(R_{2}bzam)$ group-14 tetrylenes $[M(R_{2}bzam)(HMDS)]$ $(HMDS=N(SiMe_{3})_{2};$ 1: M=Ge, R=iPr; 2: M=Si, R=tBu; 3: M=Ge, R=tBu) at 20 °C led to the monosubstituted complexes $[Co_{2}\{κ^{1}MM(R_{2}bzam)(HMDS)\}(CO)_{7}]$ (4: M=Ge, R=iPr; 5: M=Si, R=tBu; 6: M=Ge, R=tBu), which contain a terminal $κ^{1}M–tetrylene$ ligand. Whereas the $Co_{2}Si$ and $Co_{2}Ge$ tert-butyl derivatives 5 and 6 are stable at 20 °C, the $Co_{2}Ge$ isopropyl derivative 4 evolved to the ligand-bridged derivative $[Co_{2}\{μ-κ^{2}Ge,N-Ge(iPr_{2}bzam)(HMDS)\}(μ-CO)(CO)_{5}]$ (7), in which the Ge atom spans the CoCo bond and one arm of the amidinate fragment is attached to a Co atom. The mechanism of this reaction has been modeled with the help of DFT calculations, which have also demonstrated that the transformation of amidinate-tetrylene ligands on the dicobalt framework is negligibly influenced by the nature of the group-14 metal atom (Si or Ge) but is strongly dependent upon the volume of the amidinate NR groups. The disubstituted derivatives $[Co_{2}\{κ^{1}MM(R_{2}bzam)(HMDS)\}_{2}(CO)_{6}]$ (8: M=Ge, R=iPr; 9: M=Si, R=tBu; 10: M=Ge, R=tBu), which contain two terminal $κ^{1}M–tetrylene$ ligands, have been prepared by treating $[Co_{2}(CO)_{8}]$ with two equiv of 1–3 at 20 °C. The IR spectra of 8–10 have shown that the basicity of germylenes 1 and 3 is very high (comparable to that of trialkylphosphanes and 1,3-diarylimidazol-2-ylidenes), whereas that of silylene 2 is even higher.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	28
Volume Number	20
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2014-07-07
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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