Stabilization of Trans Disilyl Coordination at Square-Planar Platinum Complexes

• Published in: Organometallics Vol. 37; no. 5; pp. 720 - 728
• Main Authors: Cuevas-Chávez, Cynthia A, Zamora-Moreno, Julio, Muñoz-Hernández, Miguel A, Bijani, Christian, Sabo-Etienne, Sylviane, Montiel-Palma, Virginia
• Format: Journal Article
• Language: English
• Published: American Chemical Society 12.03.2018
• Subjects: Chemical Sciences; Coordination chemistry
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/acs.organomet.7b00566

By using two different multidentate phosphinosilyl ligands, we prepared the two platinum complexes [Pt­{PhP­((o-C6H4)­CH2SiMe2)2}­PPh3] (3) and [Pt­{P­((o-C6H4)­CH2SiMe2)2(o-C6H4)­CHSiMe2)}­PPh3] (4) exhibiting a trans configuration of the silicon atoms in a typical square-planar geometry around a Pt­(II) center. Complex 4 results from intramolecular C–H activation of a methylene moiety by the third silicon atom of the original ligand and displays an anagostic C–H···Pt interaction, as supported by solution NMR data and solid-state X-ray diffraction analysis. The reactivity of 3 toward small molecules is also discussed. In the case of H2 and CO, the corresponding dihydride [PtH2{PhP­((o-C6H4)­CH2SiMe2)2}­PPh3] (5) and dicarbonyl [Pt­{PhP­((o-C6H4)­CH2SiMe2)2}­(CO)2] (6) complexes were characterized, whereas reduction to Pt(0) and release of PPh3 and HSiMe3 were observed upon thermolysis in the presence of HBpin.