Synthesis of MII[N(SiMe3)2][Me3SiNC(tBu)NSiMe3] (M = Sn, Ge) from Amidinate Precursors: Active Catalysts for Phenyl Isocyanate Cyclization
- 17 February 2000
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 39 (5), 924-929
- https://doi.org/10.1021/ic991004b
Abstract
Mixed amidinato amido complexes [Me3SiNC(tBu)NSiMe3]M[N(SiMe3)2] (M = Sn 2, Ge 3) were prepared by the reaction of [Me3SiNC(tBu)NSiMe3]Li (1a) with SnCl2 and GeCl2(dioxane) in ether. The N(SiMe3)2 ligand in these compounds is derived from the rearrangement of the [Me3SiNC(tBu)NSiMe3]- anion with extrusion of tBuCN. The susceptibility of [Me3SiNC(tBu)NSiMe3]- to rearrangement appears to be dependent on reaction solvent and on the coordinated metal center. Single-crystal X-ray diffraction studies of 2 and 3 are presented. Replacement of Me for tBu in the ligand allowed [Me3SiNC(Me)NSiMe3]2SnII (4) to be isolated, and an X-ray structure of this compound is reported. The isolation of 4 indicates that steric factors also play a role in the stability of [Me3SiNC(tBu)NSiMe3]-. Compounds 2 and 3 are outstanding catalysts for the cyclotrimerization of phenyl isocyanates to perhydro-1,3,5-triazine-2,4,6-triones (isocyanurates) at room temperature. In contrast, complex 4 catalytically reacts with phenyl isocyanate to produce isocyanate dimer and trimer in a 52:35 ratio.Keywords
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