The heterometallic one-dimensional solvated coordination polymer [NiPt₂Cl₆(TRIP-Py)₄] _n

Abstract

The ditopic ligand 10-[4-(pyridin-4-yl)phenyl]-9-phospha-10-silatriptycene (TRIP-Py, C29H20NPSi) binds as a pyridine donor to NiII and as a phosphatriptycene donor towards PtII. The selectivity relies entirely on the Pearson character of the donor sites and the matching hardness of the respective metal cations. The product is the one-dimensional coordination polymer catena-poly[[[dichloridonickel(II)]-bis{μ-10-[4-(pyridin-4-yl)phenyl]-9-phospha-10-silatriptycene}-bis[dichloridoplatinum(II)]-bis{μ-10-[4-(pyridin-4-yl)phenyl]-9-phospha-10-silatriptycene}] dichloromethane pentasolvate ethanol icosasolvate], {[NiPt2Cl6(TRIP-Py)4]·5CH2Cl2·20EtOH} n (1), which retains large pores due to the inherent rigidity of the ligand. This is enabled by the caged triptycene scaffold which fixes the direction of the phosphorus donor with respect to the remaining molecule and especially the pyridyl moiety. In its crystal structure, which was determined from synchrotron data, the pores of the polymer are filled with dichloromethane and ethanol molecules. Finding a suitable model for the pore content is complicated as it is too disordered to give a reasonable atomic model but too ordered to be described by an electron gas solvent mask. This article presents an in-depth description of this polymer, as well as a discussion on the use of the bypass algorithm for solvent masks.

Fusing Triphenylbismuth and PnPh3 (Pn = P–Bi): Synthesis, Isolation, and Characterization of 9-Bisma-10-Pnictatriptycenes

“…Among the (di)­pnictatriptycenes, especially phosphatriptycenes, phosphaboratatriptycenes, and phosphasilatriptycenes have been employed in the fields of transition-metal catalyzed C–C cross-coupling reactions − and ortho -selective CH borylation of N-functionalized arenes, , as ditopic linkers in supramolecular chemistry − and as Bro̷nsted bases in frustrated Lewis pair (FLP) chemistry. , Moreover, azaphosphatriptycenes have been utilized as molecular gears or as ligands in the hydroformylation of internal alkenes and enol ethers . Furthermore, a derivative of III–P/Bi , 2,3,6,7,14,15-hexamethyl-9-phospha-10-bismatriptycene, has been used for the preparation of nonstabilized phosphonium ylides and exploited in Wittig reactions …”