Dawson type heteropolyanions. 1. Multinuclear ( sup 31 P, sup 51 V, sup 183 W) NMR structural investigations of octadeca(molybdotungstovanado)diphosphates. alpha. -1,2,3-(P sub 2 MM prime sub 2 W sub 15 O sub 62 ) sup n minus (M,M prime = Mo, V, W): Syntheses of new related compounds

Journal Article · Wed Apr 17 04:00:00 EDT 1991 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00008a006· OSTI ID:5641369

Abbessi, M; Contant, R; Thouvenot, R; Herve, G ^[1]

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1. Universite P. et M. Curie, Paris (France)

The mixed binary anions dimolybdopentadecatungstodiphosphate, 1,2-(P{sub 2}Mo{sub 2}W{sub 15}O{sub 61}){sup 10{minus}}, hexadecatungstodivanadodiphosphate, 1,2-(P{sub 2}V{sub 2}W{sub 16}O{sub 62}){sup 8{minus}}, and the ternary molybdotungstovanadophosphates 1,2-3-(P{sub 2}Mo{sub 2}VW{sub 15}O{sub 62}){sup 7{minus}} and 1-2,3-(P{sub 2}MoV{sub 2}W{sub 15}O{sub 62}){sup 8{minus}}, derived from the Dawson anion {alpha}-(P{sub 2}W{sub 18}O{sub 62}){sup 6{minus}} by formal substitution in one polar W{sub 3}O{sub 13} group, have been synthesized. All the octadeca(molybdotungstovanado)diphosphates {alpha}-(1,2,3)-(P{sub 2}MM{prime}{sub 2}W{sub 15}O{sub 62}){sup n{minus}} (M, M{prime} = Mo, V, W) were characterized by electrochemistry and multinuclear ({sup 31}P, {sup 51}V, {sup 183}W) solution NMR techniques. The reactivity of 4-P{sub 2}MW{sub 17} toward alkaline degradation to get P{sub 2}MW{sub 14} is discussed on this basis: vanadium(V) in the 4-location directs the departure of the W{sub 3}O{sub 13} in the other half-anion (16-18-locations) whereas molybdenum(VI) ha no directing effect. The {sup 183}W chemical shifts are discussed also in relation with the nature and the location of the substituting atoms; although considerably remote from the polar substituted site, the tungsten atoms in the opposite polar group are generally as well affected (shielded) as those directly bound ({mu}-oxo junction in the same polar group) to the substituted atom (deshielded), even in the case of the isocharge W {yields} Mo replacement. 22 refs., 7 figs., 5 tabs.

• OSTI ID: 5641369
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 30:8; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
CHEMICAL PREPARATION
DATA
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
HEAVY NUCLEI
INFORMATION
INTERMEDIATE MASS NUCLEI
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
LIGHT NUCLEI
MOLYBDENUM COMPOUNDS
NMR SPECTRA
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
OXYGEN COMPOUNDS
PHOSPHATES
PHOSPHORUS 31
PHOSPHORUS COMPOUNDS
PHOSPHORUS ISOTOPES
RADIOISOTOPES
REFRACTORY METAL COMPOUNDS
SECONDS LIVING RADIOISOTOPES
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
TUNGSTEN 183
TUNGSTEN COMPOUNDS
TUNGSTEN ISOTOPES
VANADIUM 51
VANADIUM COMPOUNDS
VANADIUM ISOTOPES