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A mixed oxo-thio-bridged tritungsten triangular cluster complex
PoIyhdron Vol. 5, No. 3, pp. 907409, Printed in Great Britain
1986 0
0277-5387/86 $3.00+ .OO 1986 Per&amon Press Ltd
COMMUNICATION A MIXED 0X0-THIO-BRIDGED ~~ANG~AR CLUSTER
TRITUNGSTEN COMPLEX
ZVI DORI* Department of Chemistry, Technion-Israel
Institute of Technology, Haifa, Israel
and F. ALBERT COTTON,*
ROSA LLUSAR and WILL1 SCHWOTZER
Department of Chemistry and Laboratory for Molecular Structure and Bonding, Texas A&M University, College Station, TX 77843, U.S.A. (Rem-bed 10 Sep~e~ff
1985; accepted 31 October 1985)
Abstract-The preparation and structural definition and UV-visible spectrum of the lW3(~,-O)3&3-S)(NCS)g]5- ion are reported. The W-W distances, averaged according to C3”virtual symmetry, are 2.612[6] A.
Tbere has recently been intense activity in the study of the cuboidal [Mo&]~+ species’-’ as well as of their important fragment, the [MO&]*” unit,8-12 and the entire serieP3*‘* ofmixed oxo-thio species, [Mo3S,04_J4’ of which there are eight, counting isomers and end members. Synthetic routes have been diverse, but it is notable that Sykes and coworkers have demonstrated the existence of a completely general route in which appropriate dinuclear species, with selected 0- and S-contents, e.g. Mo~O~~-S)~L~ are used as building blocks. Similar successful activity is not as yet in evidence for the potential tungsten analogs of these molybdenum compounds. It may also be noted that the Sykes-type synthetic route will in any case not be available because the corresponding tungsten starting materials are unavailable. Our own routes to Mo,S, and MO,& species, ‘*r ‘J which are different from those of other workers, have the advantage that they should be readily applicable to tungsten analogs as well. An exploration of this possibility has been underway for some time and reports on perthio species will be
*Authors addressed.
to
whom
correspondence
should
be
forthcoming. We wish to report here a more surprising and interesting result, namely, the isolation and structure proof of the first mixed oxothio tritungsten species,
T~gs~nhexa~r~nyl(lg)~dO.Sgof~y~o~ Na,S were refluxed, under N,, in 100 cm3 of acetic anhydride for 12 h. A red precipitate which formed upon cooling of the reaction mixture, was separated by filtration and dissolved in 0.2 M HCI. This solution was passed through a Dowex 5OW-X2 cation exchange column, washed with 0.5 M HCl and then eluted with 4 M HCI. This eluate was diluted 10 times and passed again through a cation exchanger. After washing with Hz0 the column was soaked with 0.5 M NH4SCN and left under Nz for 24 h before it was eluted. To this purple eluate propylenediamine dihydrochloride was added and after 10 days standing in air well-formed purple crystals were obtained. Because of spectral changes that occurred during this period, accompanied by the distinctive smell of H,S, we are certain that partial hydrolysis of a per&o precursor was occurring during this lOday period. The spectrum given by a solution of these purple crystals is shown in Fig. 1. The crystallographic
907
908
Communication
I
I
300
I I 400 X (nm)
I
I
I
600
500
Fig. 1. Electronic absorption spectrum of ~,~,-SX~c2-O)s(NCS)~]s-. arbitrary scale.
700
The absorbance is given on an
work* was not straightforward because the crystals have a pronounced tendency to twinning and scattered X-rays relatively poorly despite their attractive visual appearance. The [W,~z-O),~3-S~CS),15anion is shown in Fig. 2. It has effectively C,,-symmetry and the following principal dimensions (averaged accordingIy): W-W,2.612[6]A; W-S,2.34[2]A;W-0, 1.98[2] A. These may be compared with those previously reportedI for
CMO~(~~-O),~LJ-SXHNTA)~~~ -9 viz.2.589,2.360 and 1.917 A. Acknowledgement-We
Foundation Fig. 2. ORTEP representation of the cluster anion. Thermal ellipsoids are drawn at 50% probability.
*Monoclinic
crystals, P2,/c, with Q = 16.616(5) A, A, c = 23.780(10) A, fi = 109.20(2)“, Z = 4. Refinement is continuing. Current residuals are: R = 0.051, and R, = 0.066 for a fit of 253 variables to 1713 data with e > 3a(F,Z). A table of positional parameters has been deposited with the Editor at Queen Mary College and copies are available on request. b = 11.744(3)
thank
the
National
Science
for support.
REFERENCES 1. A. Mtiller, W. Eltzner, H. Biigge and R. Jostes, Angew. Chem., Znt. Ed. Engl. 1982,21,795. 2. A. MUer, W. Eltzner, W. Clegg and G. M. Sheldrick, Angew Chem., Znt. Ed. Engl. 1982,21,536. 3. T. Shibahara, H. Kuroya, K. Matsumoto and S. Ooi, J. Am. Chem. Sot. 1984,106,789.
4. T. C. W. Mak, K. S. Jasim and C. Chieh, Znorg. Chem. 1985241587. 5. P. Kathirgamanathan, M. Martinez and A. G. Sykes,
Communication In Abstracts of Fifth Climax International Conference on the Chemistry and Uses of Molybdenum, July 1985, p. 133. 6. P. Kathirgamanathan, M. Martinez and A. G. Sykes, J. Chem. Sot., Chem. Commun. 1985,953. 7. F. A. Cotton, M. P. Diebold,Z. Dori, R. Llusar and W. Schwotzer, J. Am. Chem. Sot. 1985,107,6735. 8. T. R. Halbert, K. McGauley, W.-H. Pan, R. S. Czernuszewiczand E. I. Stiefel, J. Am. Chem. Sot. 1984, 106,1849.
9. A. Miiller and U. Reinsch, Angew. Chem., Int. Ed. Engl. 1980, 19,72.
909
10. N. C. Howlader, G. P. Haight, Jr, T. W. Hambley, G. A. Lawrance, K. M. Rahrnoeller and M. R. Snow, Aust. J. Chem. 1983,36,377. 11. F. A. Cotton, Z. Dori, R. Llusar, D. 0. Marler and W. Schwotzer, Inorg. Chim. Acta 1985,102, L25. 12. F. A. Cotton, Z. Dori, R. Llusar and W. Schwotzer, J. Am. Chem. Sot. 1985,107,6734. 13. T. Shibahara, H. Hattori and H. Kuroya., J. Am. Chem. Sot. 1984,106,2710. 14. P. Kathirgamanathan, M. Martinez and A. G. Sykes, J. Chem. Sot., Chem. Commun. 1985,1437.
1986 0
0277-5387/86 $3.00+ .OO 1986 Per&amon Press Ltd
COMMUNICATION A MIXED 0X0-THIO-BRIDGED ~~ANG~AR CLUSTER
TRITUNGSTEN COMPLEX
ZVI DORI* Department of Chemistry, Technion-Israel
Institute of Technology, Haifa, Israel
and F. ALBERT COTTON,*
ROSA LLUSAR and WILL1 SCHWOTZER
Department of Chemistry and Laboratory for Molecular Structure and Bonding, Texas A&M University, College Station, TX 77843, U.S.A. (Rem-bed 10 Sep~e~ff
1985; accepted 31 October 1985)
Abstract-The preparation and structural definition and UV-visible spectrum of the lW3(~,-O)3&3-S)(NCS)g]5- ion are reported. The W-W distances, averaged according to C3”virtual symmetry, are 2.612[6] A.
Tbere has recently been intense activity in the study of the cuboidal [Mo&]~+ species’-’ as well as of their important fragment, the [MO&]*” unit,8-12 and the entire serieP3*‘* ofmixed oxo-thio species, [Mo3S,04_J4’ of which there are eight, counting isomers and end members. Synthetic routes have been diverse, but it is notable that Sykes and coworkers have demonstrated the existence of a completely general route in which appropriate dinuclear species, with selected 0- and S-contents, e.g. Mo~O~~-S)~L~ are used as building blocks. Similar successful activity is not as yet in evidence for the potential tungsten analogs of these molybdenum compounds. It may also be noted that the Sykes-type synthetic route will in any case not be available because the corresponding tungsten starting materials are unavailable. Our own routes to Mo,S, and MO,& species, ‘*r ‘J which are different from those of other workers, have the advantage that they should be readily applicable to tungsten analogs as well. An exploration of this possibility has been underway for some time and reports on perthio species will be
*Authors addressed.
to
whom
correspondence
should
be
forthcoming. We wish to report here a more surprising and interesting result, namely, the isolation and structure proof of the first mixed oxothio tritungsten species,
T~gs~nhexa~r~nyl(lg)~dO.Sgof~y~o~ Na,S were refluxed, under N,, in 100 cm3 of acetic anhydride for 12 h. A red precipitate which formed upon cooling of the reaction mixture, was separated by filtration and dissolved in 0.2 M HCI. This solution was passed through a Dowex 5OW-X2 cation exchange column, washed with 0.5 M HCl and then eluted with 4 M HCI. This eluate was diluted 10 times and passed again through a cation exchanger. After washing with Hz0 the column was soaked with 0.5 M NH4SCN and left under Nz for 24 h before it was eluted. To this purple eluate propylenediamine dihydrochloride was added and after 10 days standing in air well-formed purple crystals were obtained. Because of spectral changes that occurred during this period, accompanied by the distinctive smell of H,S, we are certain that partial hydrolysis of a per&o precursor was occurring during this lOday period. The spectrum given by a solution of these purple crystals is shown in Fig. 1. The crystallographic
907
908
Communication
I
I
300
I I 400 X (nm)
I
I
I
600
500
Fig. 1. Electronic absorption spectrum of ~,~,-SX~c2-O)s(NCS)~]s-. arbitrary scale.
700
The absorbance is given on an
work* was not straightforward because the crystals have a pronounced tendency to twinning and scattered X-rays relatively poorly despite their attractive visual appearance. The [W,~z-O),~3-S~CS),15anion is shown in Fig. 2. It has effectively C,,-symmetry and the following principal dimensions (averaged accordingIy): W-W,2.612[6]A; W-S,2.34[2]A;W-0, 1.98[2] A. These may be compared with those previously reportedI for
CMO~(~~-O),~LJ-SXHNTA)~~~ -9 viz.2.589,2.360 and 1.917 A. Acknowledgement-We
Foundation Fig. 2. ORTEP representation of the cluster anion. Thermal ellipsoids are drawn at 50% probability.
*Monoclinic
crystals, P2,/c, with Q = 16.616(5) A, A, c = 23.780(10) A, fi = 109.20(2)“, Z = 4. Refinement is continuing. Current residuals are: R = 0.051, and R, = 0.066 for a fit of 253 variables to 1713 data with e > 3a(F,Z). A table of positional parameters has been deposited with the Editor at Queen Mary College and copies are available on request. b = 11.744(3)
thank
the
National
Science
for support.
REFERENCES 1. A. Mtiller, W. Eltzner, H. Biigge and R. Jostes, Angew. Chem., Znt. Ed. Engl. 1982,21,795. 2. A. MUer, W. Eltzner, W. Clegg and G. M. Sheldrick, Angew Chem., Znt. Ed. Engl. 1982,21,536. 3. T. Shibahara, H. Kuroya, K. Matsumoto and S. Ooi, J. Am. Chem. Sot. 1984,106,789.
4. T. C. W. Mak, K. S. Jasim and C. Chieh, Znorg. Chem. 1985241587. 5. P. Kathirgamanathan, M. Martinez and A. G. Sykes,
Communication In Abstracts of Fifth Climax International Conference on the Chemistry and Uses of Molybdenum, July 1985, p. 133. 6. P. Kathirgamanathan, M. Martinez and A. G. Sykes, J. Chem. Sot., Chem. Commun. 1985,953. 7. F. A. Cotton, M. P. Diebold,Z. Dori, R. Llusar and W. Schwotzer, J. Am. Chem. Sot. 1985,107,6735. 8. T. R. Halbert, K. McGauley, W.-H. Pan, R. S. Czernuszewiczand E. I. Stiefel, J. Am. Chem. Sot. 1984, 106,1849.
9. A. Miiller and U. Reinsch, Angew. Chem., Int. Ed. Engl. 1980, 19,72.
909
10. N. C. Howlader, G. P. Haight, Jr, T. W. Hambley, G. A. Lawrance, K. M. Rahrnoeller and M. R. Snow, Aust. J. Chem. 1983,36,377. 11. F. A. Cotton, Z. Dori, R. Llusar, D. 0. Marler and W. Schwotzer, Inorg. Chim. Acta 1985,102, L25. 12. F. A. Cotton, Z. Dori, R. Llusar and W. Schwotzer, J. Am. Chem. Sot. 1985,107,6734. 13. T. Shibahara, H. Hattori and H. Kuroya., J. Am. Chem. Sot. 1984,106,2710. 14. P. Kathirgamanathan, M. Martinez and A. G. Sykes, J. Chem. Sot., Chem. Commun. 1985,1437.