Dimerization of A-alpha-[SiNb(3)W(9)O(40)](7-) by pH-controlled formation of individual Nb-mu-O-Nb linkages.

The reversible, stepwise formation of individual Nb-mu-O-Nb linkages during acid condensation of 2 equiv of A-alpha-[SiNb(3)W(9)O(40)](7-) (1) to the tri-mu-oxo-bridged structure A-alpha-[Si(2)Nb(6)W(18)O(77)](8-) (4) is demonstrated by a combination of X-ray crystallography and variable-pD solution (183)W and (29)Si NMR spectroscopy. Addition of DCl to a pD 8.4 solution of 1 (Li(+) salt in D(2)O) results in formation of a mono-Nb-mu-O-Nb-linked dimer, A-alpha-[Si(2)Nb(6)W(18)O(79)](12-) (2; pD = 3.

Triniobium Polytungstophosphates. Syntheses, Structures, Clarification of Isomerism and Reactivity in the Presence of H(2)O(2).

The reaction of K(7)[HNb(6)O(19)], H(2)O(2) and A-Na(9)[PW(9)O(34)] in water followed by treatment with Cs(+) or (n-Bu(4)N)(+) (TBA) affords the corresponding salts of the tris(peroxoniobium) heteropolyanion A,beta-[(NbO(2))(3)PW(9)O(37)](6)(-) (1) in approximately 60% isolated yields. An X-ray structure of the Cs salt, Cs1 (monoclinic P2/c; a = 16.92360(10) Å, b = 13.