Metathetical imidation of dioxobis(dimethyldithiocarbamato)molybdenum with o-substituted N-sulfinylanilines [1]

Full text of DOI:10.1023/A:1019694525719

Russian Chemical Bulletin, International Edition, Vol. 51, No. 6, pp. 1075—1076, June, 2002
1075
Letters to the Editor
Metathetical imidation of dioxobis(dimethyldithiocarbamato)molybdenum
with oꢀsubstituted Nꢀsulfinylanilines
ꢀ
D. N. Zaroubine, D. S. Holovko, and N. A. Ustynyuk
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (095) 135 5085. Eꢀmail: zaroubine@ineos.ac.ru
Scheme 1
The chemistry of transition metal imido complexes
[M]=NR, which are promising reagents for the transfer
of the imido groups, has been extensively developed in
recent years.1 In this connection, a search for new versaꢀ
tile procedures for their synthesis is an urgent problem.
Earlier, one of the main procedures, viz., the thermaly
induced metathetical replacement of the oxo ligands by
the imide ligands, has been widely used in reactions of
transition metal oxo complexes with amines,2 silylꢀ
amines,3 phosphine imines,4 and isocyanates.5,6 Howꢀ
ever, these imidating reagents are of limited usefulness.
In particular, these reagents proved to be inefficient in
imidation of thermally labile metalꢀcontaining substrates,
such as transition metal oxo dithiocarbamate complexes.6
Previously, we have reported that Nꢀsulfinylamines
are very promising imidating reagents, particularly, in
the synthesis of transition metal imido complexes, which
are inaccessible by other procedures.7 In the present study,
we demonstrated that the reaction of MoO2(S2CNMe2)2
with 2 equiv. of Nꢀsulfinyl derivatives of polyhalogenoꢀ
anilines ArNSO (Ar = 2,4,6ꢀCl3C6H2 or 2,4,6ꢀBr3C6H2)
in boiling toluene proceeded smoothly to give the correꢀ
sponding bis(arylimido) complexes 1a,b (Scheme 1).
Analogous reactions with polyalkylꢀsubstituted
Nꢀsulfinylanilines ArNSO (Ar = 2,6ꢀPri2C6H3 or
Ar = 2,4,6ꢀCl3C6H2 (a), 2,4,6ꢀBr3C6H2 (b)
i. Toluene, 110 °C, 4 h.
2,4,6ꢀMe3C6H2) proceeded more slowly to produce mixꢀ
tures of products 2—4 (Scheme 2). Along with the exꢀ
pected bis(imido) complexes 2a,b, mixed oxo imido comꢀ
plexes 3a,b and binuclear complexes 4a,b were formed
in 15—20% yields (1H NMR). This set of the reaction
products is, apparently, attributed to the low rate of forꢀ
mation of the target bis(imido) complexes 2a,b, so that
the side process giving rise to binuclear complexes 4a,b
becomes quite competitive. In the latter complexes, the
µꢀS atoms are formed through the partial transformation
of the dithiocarbamate ligands.
The results obtained in the present study demonꢀ
strate that deoxoimidation with the use of оꢀhalogenꢀ
and alkylꢀsubstituted Nꢀsulfinylanilines shows considerꢀ
able promise for the synthesis of imidobis(dimethylꢀ
dithiocarbamato)molybdenum complexes.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 987—988, June, 2002.
1066ꢀ5285/02/5106ꢀ1075 $27.00 © 2002 Plenum Publishing Corporation

1076
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 6, June, 2002
Zaroubine et al.
Scheme 2
MoO2(S2CNMe2)2 (0.59 g, 1.6 mmol) and Br3C6H2NSO (1.2 g,
3.2 mmol) in a yield of 1.14 g (72%). Found (%): C, 21.77;
H, 1.6; N, 5.6; Br, 50.2. C18H16Br6N4MoS4. Calculated (%):
C, 21.77; H, 1.6; N, 5.44; Br, 48.4. 1H NMR (400 MHz,
CDCl3), δ: 7.53 (s, 4 H, CHarom); 3.37 (s, 12 H, CH3). 13C NMR
(100 MHz, CDCl3), δ: 202.63 (CS2); 152.65, 133.7, 117.8,
115.2 (Carom); 41.06 (CH3). MS (EI, 70 eV), m/z (Irel (%)):
992 [M]+ (100), 951 (67), 909 (10), 869 (95), 665 (12), 577
(28), 329 (31), 120 (37).
This study was financially supported by the Interꢀ
national Science and Technology Center (ISTC,
Grant 1577).
References
Ar = 2,6ꢀPri2C6H3 (a), 2,4,6ꢀMe3C6H2 (b)
i. Toluene, 5 h, 110 °C.
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The MoO2(S2CNMe2)2 complex was prepared analoꢀ
gously to MoO2(S2CNEt2)2.8 NꢀSulfinylanilines ArNSO (Ar =
2,4,6ꢀCl3C6H2 or 2,4,6ꢀBr3C6H2) were synthesized according
to a known procedure.9
1
The H and 13C NMR spectra were recorded on a Bruker
AMXꢀ400 instrument. The mass spectra were measured on a
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Bis(2,4,6ꢀtrichlorophenylimido)bis(dimethyldithioꢀ
carbamato)molybdenum (1a). A solution of MoO2(S2CNMe2)2
(0.59 g, 1.6 mmol) and 2,4,6ꢀCl3C6H2NSO (0.8 g, 3.3 mmol)
in toluene (50 mL) was refluxed for 4 h, the solvent was evapoꢀ
rated, and the product was extracted with CH2Cl2 (10 mL).
After recrystallization from a CH2Cl2—hexane mixture at
–20 °C, the analytically pure darkꢀbrown product was obtained
in a yield of 1.16 g (86%). Found (%): C, 29.80; H, 2.03;
N, 7.65; Cl, 29.12. C18H16Cl6N4MoS4. Calculated (%):
C, 29.81; H, 2.22; N, 7.73; Cl, 29.33. 1H NMR (400 MHz,
CDCl3), δ: 7.15 (s, 4 H, CHarom); 3.37 (s 12 H, CH3). 13C NMR
(100 MHz, CDCl3), δ: 202.8 (CS2); 150.28, 128.47, 127.9,
127.1 (Carom); 40.58 (CH3). MS (EI, 70 eV), m/z (Irel (%)):
726 [M]+ (100), 638 (54), 606 (62), 531 (20), 120 (23).
Bis(2,4,6ꢀtribromophenylimido)bis(dimethyldithioꢀ
carbamato)molybdenum (1b) was prepared analogously from
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P. Patzschke, H. Smalla, and A. Trede, Angew. Chem. Int.
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Received March 18, 2002;
in revised form May 29, 2002