Collectively, the respective vibrational modes of the directly knitted P-Ru(PPh3)3 correspond to the spectrum of P-PPh3-Ru, indicating similar framework units and a comparable linking mode of both polyphosphines. X-ray fluorescence spectroscopy (XRF) confirms the incorporation of PPh3 into the framework (Table ). With respect to the theoretical phosphorus content of an ideally crosslinked polymer, one eighth of the initially applied phosphine amount is part of P-Ru(PPh3)3. This partial fixation within the framework can be attributed to the ability of the aromatic crosslinkers to interconnect among one another, without involving the phosphine. Accordingly, only a fraction of the Ru (1.8 wt% of the applied 7.1 wt%) is loaded on the macroligand, resulting in a molar ratio between phosphine and ruthenium of 1.5:1. Hence, numerically, it appears that the coordination sphere of the molecular ruthenium precursor with three ligating PPh3 (P:Ru = 3:1) is not retained in the solid catalyst. Similar characteristics of the incomplete involvement of PPh3 are observed for P-PPh3-Ru, where every sixth PPh3 monomer is incorporated into the framework. However, a more effective immobilization of the Ru precursor (0.79 wt% of the applied 1.0 wt%) is achieved by postsynthetic metalation of the polyphosphine. The catalysts exhibit similar isotherm shapes (IUPAC Type I and Type IV), indicating a micro-and mesoporous structure (Fig. ).