Mono- and disubstitution reactions of gyroscope like complexes derived from ClPtCl rotators within cage like dibridgehead diphosphine ligands
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© 2016 Elsevier B.V. Reaction of the gyroscope like complex (trans-1c) and p-tolSeSiMe3(3.8 equiv, 85 °C, melt) gives the disubstitution product (trans-3c, 63%) and ClSiMe3. Attempts to access a monochloride complex via monosubstitution were unsuccessful. However, when (trans-2; n = c/14, e/18) and HCl (1.0 equiv; generated from CH3COCl and excess CH3OH) are reacted, the monochloride complexes (trans-4c,e, 93–96%) are obtained. These feature dipolar rotators, a common design element in approaches to molecular gyroscopes. The crystal structures of trans-3c and trans-4c are determined, and the radii of the rotators and other geometrical features analyzed, especially with regard to the facility of PtL2rotation.
author list (cited authors)
Taher, D., Nawara-Hultzsch, A. J., Bhuvanesh, N., Hampel, F., & Gladysz, J. A.