Synthesis and Characterization of a Novel Cyclic Aluminophosphinate:  Structure and Solid-State NMR Study

We present the structure and a multinuclear solid-state NMR study of a new cyclic aluminophosphinate. The crystallographic structure of [Al2(HC6H5PO2)2(C4H9OH)8]Cl4 (compound 1) was obtained at low temperature (a = 11.830(7) Å, b = 14.216(6) Å, c = 17.790(6) Å, β = 91.25(4)°, monoclinic, P21/c, Z = 2). 13C IRCP (inversion recovery cross polarization) and NQS (non quaternary suppression) NMR experiments allowed the complete assignment of the quaternary carbon atom of the phenyl ring and the precise determination of the isotropic |1 J P - C| coupling constant. 31P CP MAS dynamics was carefully studied by varying the contact time. Dipolar oscillations even at slow MAS were observed. Up to 11 kHz, these oscillations were more pronounced, and the P−H distance was easily extracted. 27Al NMR quadrupolar parameters for 1 were obtained with very good accuracy, and unusual satellite transition splitting was observed. Furthermore, the isotropic lines of the inner and outer transitions were clearly observable, leading to the unambiguous determination of the quadrupolar parameters.