화학공학소재연구정보센터
Inorganic Chemistry, Vol.57, No.3, 1504-1516, 2018
Polyoxometalate-Assisted, One-Pot Synthesis of Pentakis[(triphenylphosphane)gold]ammonium(2+) Cation Containing Regular Trigonal-Bipyramidal Geometries of Five Bonds to Nitrdogen
Novel intercluster compounds consisting of pentakis [(triphenylphosphane)gold] ammonium (2+) cation (1) and Keggin polyoxometalate (POM) anions, i.e., {[Au(PPh3)](5)(mu(5)-N)}(3)[alpha-PM12O40](2) (1-PW for M = W; 1-PMo for M = Mo), were synthesized in 30-36% yield by one-pot reaction of the protonic acid form of the Keggin POMs, H-3[alpha-PM12O40]center dot nH(2)O (n = 13 for M = W; n = 15 for M = Mo) with monomeric (triphenylphosphane)gold(I) carboxylate [Au(RS-pyrrld)(PPh3)] [RS-Hpyrrld = (RS)-2-pyrrolidone-5-carboxylic acid] in the presence of aqueous NH3 at a molar ratio of 2:15:x (x = 3 for 1-PW; x = 7.5 for 1-PMo). These compounds resulted from the nitrogen-centered phosphanegold(I) clusterization of in situ generated monomeric phosphanegold(I) units, [Au(PPh3)](+) or [Au(L)(PPh3)](+) (L = NH3 or solvent), during the carboxylate elimination of [Au(RS-pyrrld)(PPh3)] in the presence of the Keggin POMs and aqueous NH3. The products 1-PW and 1-PMo were characterized by elemental analysis, Fourier transform infrared, thermogravimetric and differential thermal analyses (TGA/DTA), X-ray crystallography, and solid-state cross polarization magic-angle-spinning (CPMAS) (P-31 and N-15) and solution (P-31{H-1} and H-1) NMR spectroscopy. The lattice contained three independent {[Au(PPh3)](5)(mu(5)-N)}(2+) cations, of which two took regular trigonal-bipyramidal (TBP) geometries and the third took a distorted, square -pyramidal (SP) geometry. These geometries are in contrast to those reported by Schmidbaur's group for {[Au(PPh3)](3)(mu(s)-N)}(2+) cations as BF4 salts. Density functional theory and ONIOM calculations for {[(L3P)Au](n) N}((n-3)+) (L = H or Ph; n = 4-6) showed that the pentacoordinate cluster is energetically most stable and its TBP structure is only 1.6 kcal mol(-1) more stable than its SP structure, in accordance with the experimental facts.