Double Phosphates Starting with Titanium Nitride TiN Igor V. Zatovsky

(1)

A Novel Convenient Synthesis of Mixed-Valence Ti

^III

/Ti

^IV

Double Phosphates Starting with Titanium Nitride TiN Igor V. Zatovsky

^a

, Nikolay S. Slobodyanik

^a

, Denis A. Stratiychuk

^a

, Konstantin V. Domasevitch

^a

, Joachim Sieler

^b

, and Eduard B. Rusanov

^c

aInorganic Chemistry Department, Kiev University, Volodimirska Street 64, Kiev 252033, Ukraine

bInstitut für Anorganische Chemie, Universität Leipzig, Linnéstraße 3, D-04103 Leipzig, Deutschland

cInstitute of Organic Chemistry, Murmanska Street 5, Kiev 253660, Ukraine Reprint requests to I. V. Zatovsky or Dr. K. V. Domasevitch.

E-mail: dk@anorgchemie.univ.kiev.ua

Z. Naturforsch.55 b,291–298 (2000); received November 22, 1999

Melted Systems, Titanium, Double Phosphates, Mixed-valent Compounds, X-Ray Data A new synthetic approach for the low- and mixed-valence double titanium phosphates starting with titanium nitride, TiN, and based on the controlled oxidation of a low-valent metal in the phosphate melt is presented. The reaction of the system MÎ2O - P2O5 - TiN (MÎ = Na, K) in air (800-1050C) leads to loss of nitrogen, N2, and results in the formation of a number of double phosphates: KTiP2O7, K2TiÎIITiÎV(PO4)3, KTiOPO4, NaTiP2O7, NaTi2(PO4)3and a new mixed-valent diphosphate, NaTiÎIITiÎV(P2O7)2. The mixed-valent species K2TiÎIITiÎV(PO4)3

and NaTi^IIITi^IV(P2O7)2were characterized by single crystal X-ray diffraction. The described synthetic procedure is proposed as a simple and convenient method for the preparation of low- and mixed-valent phosphate materials.