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Sulphoxide compounds of ruthenium
2282
Notes
(u4+ u2) vibrations of the tetrahedral anion. Preliminary differential thermal analysis and broadline NMR experiments[4] indicate that two minor phase changes occur below 300°K and these have been attributed to hindered rotation of the methyl groups and order-disorder phenomena in the N-H"'C1 hydrogen bonding system. The spectrum at 195°K, apart from some additional weak bands between 130 and 90cm ~ shows little evidence of this ordering but at 77°K significant changes are observed; the bands at 281 and 139cm -1 are split into several components, new bands appear between 200 and 150 cm-~ and in the lattice region, eleven sharp bands are observed down to 28 cm t. These sharp spectral features are certainly indicative of substantial ordering of the DMA and chloride ions at 77°K but further analysis of the data provides little information as to the exact location of these ions in the lattice. If they were situated on the elements of symmetry required by the proposed space group then the region from 320 to 240 cm 1, where the crystal modes of vt and ~'3 are observed, should be similar to that found in the Raman spectrum of C%CuCI4 recorded at 77°K[18] where three major peaks are observed. However, this is not the case in (DMA)aCuC14 since there are at least four bands of medium to strong intensity in this region suggesting enlargement of the proposed tetramolecular unit cell at 77°K. The observed Raman frequencies for this complex, recorded at 77°K, polarization intensity for the six scattering geometries used and the proposed vibrational assignments are given in Table 7. Despite care in alignment of the crystal axes and repeated measurements, it can be seen from the intensity data that polarization leakage between diagonal and off-diagonal tensor components was very large and prevented accurate symmetry assignments; in most cases, therefore, assignments are limited to the crystal components of the CuC142- vibrations and the lattice modes. Large polarization leakage of this kind is not normally encountered in ordered crystals and must be due to inherent disorder still remaining at 77°K causing scrambling of the polarized radiation. Similar effects have been observed in the IR reflectance[19] and Raman spectral18] of (NMea)2MCI4 (M = Co, Zn, Cu) complexes recorded at 77°K; all of these complexes exhibit orientational disordering of the ions at 300°K[20].
Acknowledgements--We thank the S.R.C. and Glasgow University for equipment grants and Dr. M. Guy for helpful discussions.
Department of Chemistry University of Glasgow Glasgow G12 8QQ Scotland
HENRY A. BROWN-ACQUAYE ANDREW P. LANE
REFERENCES 1. J. T. R. Dunsmuir and A. P. Lane, J. Chem. Soc. (A), 404 (1971). 2. R. J. Clark and T. M. Dunn, J. Chem. Soc. 1198 (1963). 3. J. D. Black, J. T. R. Dunsmuir, I. W. Forrest and A. P. Lane, Inorg. Chem. 14, 1257 (1975). 4. R. D. Willet and M. L. Larsen, Inorg. Chim. Acta 5, 175 (1971). 5. H. M. Powell and A. F. Wells, J. Chem. Soc. 369 (1935). 6. G. N. Papatheodorou, J. Inorg. Nucl. Chem. 35, 465 (1973). 7. A. Engberg and H. Soling, Acta Chem. Scand. 21, 168 (1967). 8. B. N. Figgis, M. Gerloch and R. Mason, Acta Cryst. 17, 506 (1964). 9. E. Iberson, R. Gut and D. M. Gruen, J. Phys. Chem. 66, 65 (1%2). 10. R. P. van Stapele, H. G. Beliers, P. F. Bongers and H. Zijlstra, J. Chem. Phys. 44, 3719 (1966). 11. R. S. Halford, J. Chem. Phys. 14, 8 (1946). 12. T. C. Damen, S. P. S. Porto and B. Tell, Phys. Rev. 142, 570 (1966). 13. W. G. Spitzer, D. Kleinman and D. Walsh, Phys. Rev. 113, 127 (1959). 14. W. G. Spitzer and D. Kleinman, Phys. Rev. 121, 1324 (1%1). 15. J. T. R. Dunsmuir, Ph.D. Thesis, Glasgow University (1972). 16. A. Chadwick, J. T. R. Dunsmuir, S. Fernando, I. W. Forrest and A. P. Lane, J. Chem. Soc. (A), 2794 (1971). 17. I. R. Beattie, T. R. Gilson and G. A. Ozin, J. Chem. Soc. (A), 534 (1%9). 18. H. A. Brown-Acquaye and A. P. Lane, unpublished results. 19. J. T. R. Dunsmuir and A. P. Lane, J. Chem. Soc. (A), 2781 (1971). 20. J. R. Wiesner, R. C. Srivastara, C. H. Kennard, M. DiVaira and E. C. Lingafelter, Acta Cryst. 23, 565 (1967).
£ inorg,nucl.Chem.,1977,Vol.39.pp. 2282-2283. PergamonPress. Printedin GreatBritain Sulphoxide compounds of ruthenium (Received 28 April 1977) Dialkyl sulphoxides namely di-n-propyl, di-n-butyl sulphoxides (Pr2"SO and Bu2"SO) and cyclic sulphoxides such as tetramethylene sulphoxide (TMSO) are known to form complexes with many transition elements including platinum(II) and palladium(II)[1-4]. In this note some ruthenium sulphoxides complexes are reported.
EXPERIMENTAL RuC13'xH20 (JM) was treated several times with concentrated hydrochloric acid before use. RuBr3.xH20 was prepared from freshly precipitated "hydrated ruthenium oxide" from RuC13xH20 and KOH(GR). Di-n-propyl sulphoxide (Pr2"SO), dim-butyl snlphoxide (Bu2~SO) and tetramethylene sulphoxide (TMSO) obtained from Aldrich Chemicals (U.S.A.) were used directly. Dihalotetrakis (tetramethyiene sulphoxide) ruthenium(II), Ru(TMSO)4X2 (X=CI, Br), were prepared by refluxing a mixture of 1 ml of TMSO and 0.3-0.5 g of RuX3.xH20 in alcohol. Crystals were obtained on concentrating the solution. Trihalotris (di-n-butyisulphoxide) ruthenium(III), Ru(Bu2" SO)3X3 were prepared by the same method using Buz"SO instead of TMSO. The compounds were, however, separated by adding
ether to the concentrated solutions. In case of trichlorotris (di-npropylsulphoxide) ruthenium(Ill), Ru(Pr2"SO)~C13, ruthenium chloride was first dissolved in a few ml of acetone and after adding a little Pr2"SO, the mixture was refluxed. Later, acetone was evaporated off--the mass dissolved in absolute alcohol and the product precipitated by adding ether. The bromo derivative, Ru(Pr2"SO)3Br3 was prepared by directly digesting RuBrfxH20 in Prz"SO and heating the mixture. On standing, the desired compound separated. From elemental analysis (CSIRO, Australia), IR data (Specord IR 75) and conductance measurements (Philip's Conductivity Bridge, PR 9500), all the compounds appear to be 6-coordinated non-electrolytes (Table 1).
RESULTS AND DISCUSSION IR data especially the shifts of sulphoxide stretching frequencies indicate the bonding in sulphoxide compounds[l,4]. In Ru(TMSO)4X2, ~so frequencies occur at 1125 and 1065cm -t whereas in free TMSO it appears at 1021 cm-t. This increase indicates the presence of entirely S bonded TMSO. For Ru(R2SO)3X3, the S-O stretches (Vs_o= 1017 cm 1 and 1030 cm-I for free Pr2"SO and Bu2"SO respectively[l]) are found at both
Notes
2283
Table 1. Elemental analyses, physical data and some important 1R frequencies of ruthenium sulphoxide compounds Decomposition temperature (°C)
Elemental
Analyses
C
H
X
Found (Calc)
Found (Calc)
Found (Calc)
vsot in cm ~ PR,, s and *'~,, ~, {Donor atom) in cm '
33.05 (~2.641 28.50 (28.36) 15.38 {35.43) 29.45 (29.07) 41.7 (41.52) 34.40 (34.82)
5.48 (5.47) 4.50 14.761 6.7t! (6.94i 5.96 15.69! 7.76 (7.84) 6.20 (5.84)
12.60 (12.64) 23.80 123.58) 17.27 (17.47) 31.911 (32.64) 15.10 115.311 28.8// (28.961
1125vs, 1065vs(S)
Compounds
Colour
Ru(TMSO)4C1,
Light yellow
180
RtdTMSOIaBr~
Bright yellow
195
Ru(Pre'~SOi~Cla
Orange red
110
Ru(Pr:"SOl~Br~
Dirt; yellow
127
Ru(Bue"S()hCI 3
Orange red
120
Ru(Bu2"S())~Br~
Light yellow
130
(%l
11305. 1065vs($1 11155, 110551SI 9405(O) 11205($1 950510) 1125s(S) 9505(O) 1100s(S) 980(0)
450ms "~205, 500sh 460m, 4555h 510s 460w 505ms 440m 485ms
+In Nujol mull. Vso for free TMSO. Pr2"SO and Bue"SO are 1021vs[8]. 1017vs[I] and 1030vs[ll respectively, vs, very strong: s. strong: ms, medium strong: m, medium; w, weak. X, C1, Br.
higher and lower frequencies (Table 1). These shifts show thai the ligands' are coordinated to Ru(lll) through both the donor atoms. This is further supported by the presence of the bands at ~500cm i iVR°_O) and 450cm i (YR,-S) in the spectra of Ru(R2SO)~X~. Similar mixed bonding has been reported in PI(ll) and Pd(ll) complexes[4, 81. While dimetbyl sulphoxide (DMSO) yields both Ru(Ill! and Ru{ll) complexes[5-7], TMSO prefers coordination with Ru{II) and the dialkyl sulphoxides Ru(lll).
D@artment of Chemistry Dibrugarh Unicersity Dibrn~carh -786004 Assam India
T. BORA M.M. SINGH*
REFERENCES 1. W. F. Currier and J. H. Weber. lnor~. Chem. 6. 1539 {19671. 2. P. W. N, M. Van Leeuwen. Inorganic Complexe~ of Lij,ands Containing the Thionyl Group, Thesis, Leiden 119671. 3. B. B. Wayland and R. F. Schramm, lnor.e. Chem. 8,971 ii[9691. 4. J. H. Price, A. N. Williamson, R. F. Schramm and B. B. Wayland, hwr¢. Chem. I1, 1280 11972~. 5. T. Bora and M. M. Singh, J hwr~,,. Nucl. ('hem. 38, 1815 ( 19761. 6. I. P. Evans, A. Spencer and G. Wilkinson, J ('hem. So¢. (Dalton Trans.) 204 119731. 7. f. Bora and M M. Singh, Zhur. Neorg. Khim 20. 419 (19751. 8. ,I. H. Price, R. F. Schramm and B. B. Wavland. Chem Commun. 1~77 (1970~.
d in,re nucl Ugem.197" Vol 39, pp 22832284, PergamonPres,. Printedin GreatBritain
Iso-thiocyanato complexes of manganese(II) with urea and derivatives (Received 5 April 1977i We have previously reported on the preparation and structure of high-spin coordination compounds of Mn(II) halides with urea (U)[1], N,N'-dimethylurea (DMU)[2] and N,N'-diethylurea (DEU)[3]. Up to now the coordination of Mn(II) thiocyanate with the same ligands was unknown except for the trans octahedral Mn Ua(NCS)z compound [4] in which the urea ligands are bonded through the oxygen atom and the thiocyanato group through nitrogen. We decided to investigate more completely this field, with the three ligands mentioned above.
EXPERIMENTAL The ligands were recrystallized from water. Mn(lI) thiocyanate was obtained after reaction of Ba(SCN) 2 with Mn SQ. All preparations were done in anhydrous ethanol under a stream of nitrogen; triethylorthoformate was added to eliminate all traces of water [5].
Diisothiocyanatotetrakis (ligand) manganese(Ill. A solution with the ligand (0.035 mole) and Mn(NCSL, (0.005mole) was stirred and retluxed during 4 hr. For the substituted ureas, the solution was evaporated to a sma!! volume and the crystallization was induced by diethylether. In the case of urea, after a small addition of diethylether, the solid product appeared after several hours. Oiisothiocyunato-octaki~ (urea) manganese(ll): An addition of diethylethm in solutions refluxed for 10 rain and stirred for several hours at room temperature, when the ratios urea/metal were higher than eight, always yielded this compound. All these white solids were washed with diethylether and dried under vacuum (0.2 ram). Analytical and physical methods. They have been previously described[3, 61. Analysis are given hereunder:
"Fable 1. Analytical results
Compound Mn DEU4(NCS)2 Mn DMU41NCS)2 Mn Ua(NCS) 2 Mn U~(NCSb
M.p. (°C)
Calc.
C% Found
Calc.
H% Found
71° 670 141° 120°
41.56 41.55 3 2 . 1 2 32.16 1 7 . 5 2 17.64 18.43 18.54
7.61 6.16 3.92 4.95
7.61 6.17 4.06 5.13
Calc,
NC~ Found
22.03 26.75 34.05 38.70
21.87 26.81 34.12 38.74
Mn% Calc. Found 8.6 10.5 13.4 8.4
8.7 10.5 13.3 8.3
Notes
(u4+ u2) vibrations of the tetrahedral anion. Preliminary differential thermal analysis and broadline NMR experiments[4] indicate that two minor phase changes occur below 300°K and these have been attributed to hindered rotation of the methyl groups and order-disorder phenomena in the N-H"'C1 hydrogen bonding system. The spectrum at 195°K, apart from some additional weak bands between 130 and 90cm ~ shows little evidence of this ordering but at 77°K significant changes are observed; the bands at 281 and 139cm -1 are split into several components, new bands appear between 200 and 150 cm-~ and in the lattice region, eleven sharp bands are observed down to 28 cm t. These sharp spectral features are certainly indicative of substantial ordering of the DMA and chloride ions at 77°K but further analysis of the data provides little information as to the exact location of these ions in the lattice. If they were situated on the elements of symmetry required by the proposed space group then the region from 320 to 240 cm 1, where the crystal modes of vt and ~'3 are observed, should be similar to that found in the Raman spectrum of C%CuCI4 recorded at 77°K[18] where three major peaks are observed. However, this is not the case in (DMA)aCuC14 since there are at least four bands of medium to strong intensity in this region suggesting enlargement of the proposed tetramolecular unit cell at 77°K. The observed Raman frequencies for this complex, recorded at 77°K, polarization intensity for the six scattering geometries used and the proposed vibrational assignments are given in Table 7. Despite care in alignment of the crystal axes and repeated measurements, it can be seen from the intensity data that polarization leakage between diagonal and off-diagonal tensor components was very large and prevented accurate symmetry assignments; in most cases, therefore, assignments are limited to the crystal components of the CuC142- vibrations and the lattice modes. Large polarization leakage of this kind is not normally encountered in ordered crystals and must be due to inherent disorder still remaining at 77°K causing scrambling of the polarized radiation. Similar effects have been observed in the IR reflectance[19] and Raman spectral18] of (NMea)2MCI4 (M = Co, Zn, Cu) complexes recorded at 77°K; all of these complexes exhibit orientational disordering of the ions at 300°K[20].
Acknowledgements--We thank the S.R.C. and Glasgow University for equipment grants and Dr. M. Guy for helpful discussions.
Department of Chemistry University of Glasgow Glasgow G12 8QQ Scotland
HENRY A. BROWN-ACQUAYE ANDREW P. LANE
REFERENCES 1. J. T. R. Dunsmuir and A. P. Lane, J. Chem. Soc. (A), 404 (1971). 2. R. J. Clark and T. M. Dunn, J. Chem. Soc. 1198 (1963). 3. J. D. Black, J. T. R. Dunsmuir, I. W. Forrest and A. P. Lane, Inorg. Chem. 14, 1257 (1975). 4. R. D. Willet and M. L. Larsen, Inorg. Chim. Acta 5, 175 (1971). 5. H. M. Powell and A. F. Wells, J. Chem. Soc. 369 (1935). 6. G. N. Papatheodorou, J. Inorg. Nucl. Chem. 35, 465 (1973). 7. A. Engberg and H. Soling, Acta Chem. Scand. 21, 168 (1967). 8. B. N. Figgis, M. Gerloch and R. Mason, Acta Cryst. 17, 506 (1964). 9. E. Iberson, R. Gut and D. M. Gruen, J. Phys. Chem. 66, 65 (1%2). 10. R. P. van Stapele, H. G. Beliers, P. F. Bongers and H. Zijlstra, J. Chem. Phys. 44, 3719 (1966). 11. R. S. Halford, J. Chem. Phys. 14, 8 (1946). 12. T. C. Damen, S. P. S. Porto and B. Tell, Phys. Rev. 142, 570 (1966). 13. W. G. Spitzer, D. Kleinman and D. Walsh, Phys. Rev. 113, 127 (1959). 14. W. G. Spitzer and D. Kleinman, Phys. Rev. 121, 1324 (1%1). 15. J. T. R. Dunsmuir, Ph.D. Thesis, Glasgow University (1972). 16. A. Chadwick, J. T. R. Dunsmuir, S. Fernando, I. W. Forrest and A. P. Lane, J. Chem. Soc. (A), 2794 (1971). 17. I. R. Beattie, T. R. Gilson and G. A. Ozin, J. Chem. Soc. (A), 534 (1%9). 18. H. A. Brown-Acquaye and A. P. Lane, unpublished results. 19. J. T. R. Dunsmuir and A. P. Lane, J. Chem. Soc. (A), 2781 (1971). 20. J. R. Wiesner, R. C. Srivastara, C. H. Kennard, M. DiVaira and E. C. Lingafelter, Acta Cryst. 23, 565 (1967).
£ inorg,nucl.Chem.,1977,Vol.39.pp. 2282-2283. PergamonPress. Printedin GreatBritain Sulphoxide compounds of ruthenium (Received 28 April 1977) Dialkyl sulphoxides namely di-n-propyl, di-n-butyl sulphoxides (Pr2"SO and Bu2"SO) and cyclic sulphoxides such as tetramethylene sulphoxide (TMSO) are known to form complexes with many transition elements including platinum(II) and palladium(II)[1-4]. In this note some ruthenium sulphoxides complexes are reported.
EXPERIMENTAL RuC13'xH20 (JM) was treated several times with concentrated hydrochloric acid before use. RuBr3.xH20 was prepared from freshly precipitated "hydrated ruthenium oxide" from RuC13xH20 and KOH(GR). Di-n-propyl sulphoxide (Pr2"SO), dim-butyl snlphoxide (Bu2~SO) and tetramethylene sulphoxide (TMSO) obtained from Aldrich Chemicals (U.S.A.) were used directly. Dihalotetrakis (tetramethyiene sulphoxide) ruthenium(II), Ru(TMSO)4X2 (X=CI, Br), were prepared by refluxing a mixture of 1 ml of TMSO and 0.3-0.5 g of RuX3.xH20 in alcohol. Crystals were obtained on concentrating the solution. Trihalotris (di-n-butyisulphoxide) ruthenium(III), Ru(Bu2" SO)3X3 were prepared by the same method using Buz"SO instead of TMSO. The compounds were, however, separated by adding
ether to the concentrated solutions. In case of trichlorotris (di-npropylsulphoxide) ruthenium(Ill), Ru(Pr2"SO)~C13, ruthenium chloride was first dissolved in a few ml of acetone and after adding a little Pr2"SO, the mixture was refluxed. Later, acetone was evaporated off--the mass dissolved in absolute alcohol and the product precipitated by adding ether. The bromo derivative, Ru(Pr2"SO)3Br3 was prepared by directly digesting RuBrfxH20 in Prz"SO and heating the mixture. On standing, the desired compound separated. From elemental analysis (CSIRO, Australia), IR data (Specord IR 75) and conductance measurements (Philip's Conductivity Bridge, PR 9500), all the compounds appear to be 6-coordinated non-electrolytes (Table 1).
RESULTS AND DISCUSSION IR data especially the shifts of sulphoxide stretching frequencies indicate the bonding in sulphoxide compounds[l,4]. In Ru(TMSO)4X2, ~so frequencies occur at 1125 and 1065cm -t whereas in free TMSO it appears at 1021 cm-t. This increase indicates the presence of entirely S bonded TMSO. For Ru(R2SO)3X3, the S-O stretches (Vs_o= 1017 cm 1 and 1030 cm-I for free Pr2"SO and Bu2"SO respectively[l]) are found at both
Notes
2283
Table 1. Elemental analyses, physical data and some important 1R frequencies of ruthenium sulphoxide compounds Decomposition temperature (°C)
Elemental
Analyses
C
H
X
Found (Calc)
Found (Calc)
Found (Calc)
vsot in cm ~ PR,, s and *'~,, ~, {Donor atom) in cm '
33.05 (~2.641 28.50 (28.36) 15.38 {35.43) 29.45 (29.07) 41.7 (41.52) 34.40 (34.82)
5.48 (5.47) 4.50 14.761 6.7t! (6.94i 5.96 15.69! 7.76 (7.84) 6.20 (5.84)
12.60 (12.64) 23.80 123.58) 17.27 (17.47) 31.911 (32.64) 15.10 115.311 28.8// (28.961
1125vs, 1065vs(S)
Compounds
Colour
Ru(TMSO)4C1,
Light yellow
180
RtdTMSOIaBr~
Bright yellow
195
Ru(Pre'~SOi~Cla
Orange red
110
Ru(Pr:"SOl~Br~
Dirt; yellow
127
Ru(Bue"S()hCI 3
Orange red
120
Ru(Bu2"S())~Br~
Light yellow
130
(%l
11305. 1065vs($1 11155, 110551SI 9405(O) 11205($1 950510) 1125s(S) 9505(O) 1100s(S) 980(0)
450ms "~205, 500sh 460m, 4555h 510s 460w 505ms 440m 485ms
+In Nujol mull. Vso for free TMSO. Pr2"SO and Bue"SO are 1021vs[8]. 1017vs[I] and 1030vs[ll respectively, vs, very strong: s. strong: ms, medium strong: m, medium; w, weak. X, C1, Br.
higher and lower frequencies (Table 1). These shifts show thai the ligands' are coordinated to Ru(lll) through both the donor atoms. This is further supported by the presence of the bands at ~500cm i iVR°_O) and 450cm i (YR,-S) in the spectra of Ru(R2SO)~X~. Similar mixed bonding has been reported in PI(ll) and Pd(ll) complexes[4, 81. While dimetbyl sulphoxide (DMSO) yields both Ru(Ill! and Ru{ll) complexes[5-7], TMSO prefers coordination with Ru{II) and the dialkyl sulphoxides Ru(lll).
D@artment of Chemistry Dibrugarh Unicersity Dibrn~carh -786004 Assam India
T. BORA M.M. SINGH*
REFERENCES 1. W. F. Currier and J. H. Weber. lnor~. Chem. 6. 1539 {19671. 2. P. W. N, M. Van Leeuwen. Inorganic Complexe~ of Lij,ands Containing the Thionyl Group, Thesis, Leiden 119671. 3. B. B. Wayland and R. F. Schramm, lnor.e. Chem. 8,971 ii[9691. 4. J. H. Price, A. N. Williamson, R. F. Schramm and B. B. Wayland, hwr¢. Chem. I1, 1280 11972~. 5. T. Bora and M. M. Singh, J hwr~,,. Nucl. ('hem. 38, 1815 ( 19761. 6. I. P. Evans, A. Spencer and G. Wilkinson, J ('hem. So¢. (Dalton Trans.) 204 119731. 7. f. Bora and M M. Singh, Zhur. Neorg. Khim 20. 419 (19751. 8. ,I. H. Price, R. F. Schramm and B. B. Wavland. Chem Commun. 1~77 (1970~.
d in,re nucl Ugem.197" Vol 39, pp 22832284, PergamonPres,. Printedin GreatBritain
Iso-thiocyanato complexes of manganese(II) with urea and derivatives (Received 5 April 1977i We have previously reported on the preparation and structure of high-spin coordination compounds of Mn(II) halides with urea (U)[1], N,N'-dimethylurea (DMU)[2] and N,N'-diethylurea (DEU)[3]. Up to now the coordination of Mn(II) thiocyanate with the same ligands was unknown except for the trans octahedral Mn Ua(NCS)z compound [4] in which the urea ligands are bonded through the oxygen atom and the thiocyanato group through nitrogen. We decided to investigate more completely this field, with the three ligands mentioned above.
EXPERIMENTAL The ligands were recrystallized from water. Mn(lI) thiocyanate was obtained after reaction of Ba(SCN) 2 with Mn SQ. All preparations were done in anhydrous ethanol under a stream of nitrogen; triethylorthoformate was added to eliminate all traces of water [5].
Diisothiocyanatotetrakis (ligand) manganese(Ill. A solution with the ligand (0.035 mole) and Mn(NCSL, (0.005mole) was stirred and retluxed during 4 hr. For the substituted ureas, the solution was evaporated to a sma!! volume and the crystallization was induced by diethylether. In the case of urea, after a small addition of diethylether, the solid product appeared after several hours. Oiisothiocyunato-octaki~ (urea) manganese(ll): An addition of diethylethm in solutions refluxed for 10 rain and stirred for several hours at room temperature, when the ratios urea/metal were higher than eight, always yielded this compound. All these white solids were washed with diethylether and dried under vacuum (0.2 ram). Analytical and physical methods. They have been previously described[3, 61. Analysis are given hereunder:
"Fable 1. Analytical results
Compound Mn DEU4(NCS)2 Mn DMU41NCS)2 Mn Ua(NCS) 2 Mn U~(NCSb
M.p. (°C)
Calc.
C% Found
Calc.
H% Found
71° 670 141° 120°
41.56 41.55 3 2 . 1 2 32.16 1 7 . 5 2 17.64 18.43 18.54
7.61 6.16 3.92 4.95
7.61 6.17 4.06 5.13
Calc,
NC~ Found
22.03 26.75 34.05 38.70
21.87 26.81 34.12 38.74
Mn% Calc. Found 8.6 10.5 13.4 8.4
8.7 10.5 13.3 8.3