How Solid Surfaces Control Stability and Interactions of Supported Cationic CuI(dppf) Complexes─A Solid-State NMR Study.

Organometallic complexes are frequently deposited on solid surfaces, but little is known about how the resulting complex-solid interactions alter their properties. Here, a series of complexes of the type Cu(dppf)(Lx)+ (dppf = 1,1'-bis(diphenylphosphino)ferrocene, Lx = mono- and bidentate ligands) were synthesized, physisorbed, ion-exchanged, or covalently immobilized on solid surfaces and investigated by 31P MAS NMR spectroscopy. Complexes adsorbed on silica interacted weakly and were stable, while adsorption on acidic γ-Al2O3 resulted in slow complex decomposition. Ion exchange into mesoporous Na-[Al]SBA-15 resulted in magnetic inequivalence of 31P nuclei verified by 31P-31P RFDR and 1H-31P FSLG HETCOR. DFT calculations verified that a MeCN ligand dissociates upon ion exchange. Covalent immobilization via organic linkers as well as ion exchange with bidentate ligands both lead to rigidly bound complexes that cause broad 31P CSA tensors. We thus demonstrate how the interactions between complexes and functional surfaces determine and alter the stability of complexes. The applied Cu(dppf)(Lx)+ complex family members are identified as suitable solid-state NMR probes for investigating the influence of support surfaces on deposited inorganic complexes.

Quantitative Distinction between Noble Metals Located in Mesopores from Those on the External Surface.

We compare three methods for quantitatively distinguishing the location of noble metal (NM) particles in mesopores from those found on the external support surface. MCM-41 and SBA-15 with NM located in mesopores or on the external surface were prepared and characterized by TEM. 31 P MAS NMR spectroscopy was used to quantify arylphosphines in complexes with NM. Phosphine/NM ratios drop from 2.0 to 0.2 when increasing the probe diameter from 1.08 to 1.54 nm. The reaction between NM and triphenylphosphine (TPP) within 3.0 nm MCM-41 pores takes due to confinement effects multiple weeks. In contrast, external NM react with TPP instantly. A promising method is filling the pores by using the pore volume impregnation technique with tetraethylorthosilicate (TEOS). TPP loading revealed that 66 % of NMs are located on the external surface of MCM-41. The pore filling method can be used in association with any probe molecule, also for the quantification of acid sites.