Complexation of beryllium(II) ion by phosphinate ligands in aqueous solution. Synthesis and XRPD structure determination of Be[(PhPO2)2CH2](H2O)2.
Two bifunctional ligands, phenyl(carboxymethyl)phosphinate (ccp(2-) and P,P'-diphenylmethylenediphosphinate (pcp(2-)), have been tested as chelating agents of beryllium(II). Both ligands have the same charge and a similar chelating structure, but whereas the 1:1 adduct of pcp(2-), Be(pcp)(H(2)O)(2), could be isolated as a white powder, no pure compound could be isolated from solutions containing beryllium(II) and ccp(2-). Instead, the solutions were examined by means of potentiometry and (9)Be NMR spectroscopy. Analysis of the potentiometric titration data with the program HYPERQUAD suggested the formation of the complex species BeL, [BeHL](+), [BeL(2)](2-), and [BeHL(2)](-) (L = ccp). The formation constants for these species were determined at 25 degrees C and I = 0.5 mol dm(-3) NaClO(4). The (9)Be NMR spectra are consistent with this model. The formation constants found for the ccp(2-) complexes are lower than those reported for related phosphonate ligands. However, the effective stability constant (which gives a better indication of the intrinsic coordinating capacity of the ligand at a particular pH) of the complex [Be(ccp)(2)](2-) at pH < 4 is greater than the effective constants of the corresponding phosphonoacetate and methylenediphosphonate complexes. The structure of Be(pcp)(H(2)O)(2) was determined by X-ray powder diffraction methods and consists of discrete molecules interconnected by an extended 2D network of hydrogen bonds, resulting in a stacking of doublelayers with a polar core and a lipophilic surface. Crystal data: C(13)H(16)BeO(6)P(2), fw 339.21, monoclinic P2(1)/c, a = 16.174(1) A, b = 8.979(1) A, c = 10.929(1) A, beta = 90.398(9) degrees, V = 1587.2(3) A(3), Z = 4.
Cecconi
Franco
F
Istituto della Chimica dei Composti Organometallici, CNR (ICCOM-CNR), Via J. Nardi 39, I-50132 Firenze, Italy.
Dominguez
Sixto
S
Masciocchi
Norberto
N
Midollini
Stefano
S
Sironi
Angelo
A
Vacca
Alberto
A