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Young1995 PDF
Young1995 PDF
An Experiment
Charles G. Young
University of Melbourne, Parkville 3052, Australia
Metal oxides are important industrial catalysts (1) and
certain biological systems, notably those containing Mn,
Fe and Mo, exploit 0x0-metal active sites in a wide variety
of catalytic reactions (2). Indeed, the high-valent chemis-
try of the early and middle transition metals is dominated
by 0x0 complexes (3).Diverse and important, oxomolybde-
num chemistry is particularly instructive and relevant in
undergraduate inorganic chemistry (4). I t forms the basis
of this undergraduate experiment.
The 0x0 lieand.
- , formallv 02-. -
stabilizes high-valent met-
al centers by both o-and ;-bask interactions and is suscep-
tible to both nucleo~hilicand electro~hilicattack. Nncleo-
philic attack by phkphine on a d i o x o - ~ o (center
~ ~ ) leads
to oxygen atom transfer (51, two-electron reduction of mo-
lybdenum and concomitant oxidation of phosphorus (eq 1).
1 ~+
[ ~ 0 ~ ' 0+~:PR, + [ M O ~ O+ ]OPR,
~~ (1)
data are summarized after the synthesis of each com- 7. Moore. F. W.: Larson.M. L.Inore. Cham 1967.6998 . .
8. C h e n , ~J.-J.:
. d ,W.:~ewton,W E. hrorg Chem 1976,15,2612.
M e ~ o ~ a lJ.
pound.] From analytical and (simdated) mass spectral 9. (a1 Barral, R.: Bocard, C.: Seree de Rah, I.; SaJus, L. 72tmhsdron Lett 1972, 1693.
data students are able to determine the empirical and mo- (bl Balral, R.:B a d C.; Seree de Roch, I.; Sajus, L. Kine'. Coloi. iEngl. Trans.)
lecular formulae of the compounds. Having established the ....
1979 ,.l d., . ...
i?"
10. Reynolds, M.S.:Berg, J.M.; Holm, R. H. Inorg Chem 1984.23,3057.
formulas, infrared and nuclear magnetic resonance spec- 11. in) Ricard. L : Estienne, J.; Koraglannids. P: Taledano, E:Fiseher, J ; Mitsch1er.A.;
tra are examined and molecular structures deduced. Infra- Weirs. R. J. Cnoid. C h i . 1914.3, 277. tbi Berg, J.;Hodgson, K 0.in or^ Chem.
red spectra exhibit bands due to the dithiocarbamate (typi- 1980,19,2180.
12. Dirand, J.:Rieard. L.;Weirr,R. J. Chem Soc..DoIton P a n s 1976,278.
call v(CN) 1550-1500 cm-'1 and 0x0 (v(Mo=O) 1000-850
cm-3 ) hgands
. 13. Y m . X F.;Young,C. G A u a r . J. Chem 1991,44.361.
a s well a s co-ligands such as K-0and szZ- 14. Newton. W E.: McDonald, J. W J. las+Commort Mstols 1977.54, 51.