Synthesis and structural characterization of novel neutral hexacoordinate silicon(IV) complexes with SiO2N4 skeletons containing cyanato-N or thiocyanato-N ligands.
A series of novel hexacoordinate silicon(IV) complexes with an SiO2N4 skeleton (compounds (OC-6-12)-3, (OC-6-12)-4, (OC-6-12)-5, (OC-6-12)-6, and (OC-6-2'2)-7) were synthesized, starting from Si(NCO)4 or Si(NCS)4. These compounds contain (i) two bidentate O,N-chelate ligands (or one tetradentate O,N,N,O-chelate ligand) derived from 4-aminopent-3-en-2-ones of the formula type Me-C(NRH)=CH-C(O)-Me (R = organyl) and (ii) two monodentate cyanato-N or thiocyanato-N ligands. Formally, the bidentate singly negatively charged O,N-chelate ligands (tetradentate 2-fold negatively charged O,N,N,O-chelate ligand) behave as ligands of the imino-enolato type. In addition, the adduct trans-8 was synthesized by reaction of Si(NCS)4 with 2 molar equiv of Me-C(Ni-PrH)=CH-C(O)-Me. This hexacoordinate silicon(IV) complex contains (i) four monodentate thiocyanato-N ligands and (ii) two neutral monodentate ligands of the iminio-enolato type. All compounds synthesized were structurally characterized by single-crystal X-ray diffraction and solid-state and solution NMR spectroscopy. To get more information about the stereochemistry of these compounds, the experimental investigations were complemented by computational studies.
Seiler
Oliver
O
Institut für Anorganische Chemie, Universität Würzburg, Am Hubland, D-97074 Würzburg, Germany.
Burschka
Christian
C
Fischer
Markus
M
Penka
Martin
M
Tacke
Reinhold
R