- Email: [email protected]
Mononuclear pyridine-2-thionato complexes formed directly from ruthenium trichloride
Polyhedron Vol. 10, No. 8, pp. 837440, 1991 Printed in Great Britain
0
0277-5387/91 %3.00+.00 1991 Pergamon Press plc
MONONUCLEAR PYRIDINE-2-THIONA’ COMPLEXES FORMED DIRECTLY FROM RUTHENIUM TRICHLORIDE ANTONY J. DEEMING* and MANZURUL KARIM Department of Chemistry, University College London, 20 Gordon Street, London WClH OAJ, U.K. (Received 21 August 1990 ; accepted 4 January 1991)
Abstract-Reductive carbonylation of ruthenium trichloride in refluxing 2-methoxyethanol leads to a chlorocarbonyl complex of ruthenium(I1) which reacts directly with pyridine-2thione (pySH) to give high yields of [Ru(pyS),(CO),], and the 6-methylpyridine-2-thionato analogue is prepared similarly but in much lower yield. Quinoline-2-thione (quinSH) gives high yields of the compound [RuCl,(quinSH),(CO),] and only low yields of the dehydrochlorination compound [Ru(quinS),(CO),]. The more crowded thione, 4,8-dimethylquinoline-Zthione, gives only the chloro complexes and no dehydrochlorination.
Ruthenium(I1) chlorocarbonyl complexes are easily synthesized by treating ruthenium trichloride with carbon monoxide in refluxing alcoholic solvents, followed by the addition of a neutral ligand.’ For example, tertiary phosphine complexes such as [RuCl,(CO),L,] are readily synthesized in this way.‘,’ We wished to synthesize mononuclear pyridine-2-thionato complexes of ruthenium as starting materials for the synthesis of cluster and cage compounds, for example, we have synthesized the 2-pyridyl clusters [Ru,(S),(C,H,N),(CO), ,] and [Rus(S)&H~N)l(CO),,l from [Ru(pyS)z(CO),l and [Ru,(CO),,],~ and these results will be reported later. We originally synthesized [Ru(pyS),(CO),] from [Ru~(CO),~] and an excess of pySH under vigorous conditions4 but we sought a good easy route from RuCl, * 3H,O and this method is described herein. RESULTS AND DISCUSSION It is well known that bubbling carbon monoxide through a refluxing solution of ruthenium trichloride in 2-methoxyethanol gives a yellow solution containing reactive ruthenium(I1) chlorocarbony1 species.’ Probably the major one present is ,fac-[RuCl,(CO),]-. These solutions are valuable in the synthesis of ruthenium(I1) species and tertiary phosphines, arsines, amines, pyridine (L), etc., give
*Author to whom correspondence
should be addressed.
[RuC~~(CO)~L~] or [RuC12(CO)L3] in different stereochemistries.‘,* Ruthenium(I1) pyridine-2-thione (pySH) or thionato (pyS) complexes have been prepared previously from tertiary phosphine-containing precursors and all contain tertiary phosphines, e.g. [Ru(pyS),(CO)(PPh,)l, [RuH(pyS)(CO)(PPh,),, [Ru (pyS),(CO),(PPh,)l, [RuHCl(pySH)(CO)(PPh,)1, or [RuCl(pyS)(pySH)(CO)(PPh3)2].~7 These complexes contain pyS as a monodentate S-bonded or chelating ligand or pySH as a S-bonded neutral thione ligand. In looking for a straightforward route to [Ru (‘pyS),(CO),] from RuCl, - 3H20, we found that treatment of the 2-methoxyethanol solution containing ruthenium(I1) chlorocarbonyl species with pySH, followed by thermal dehydrochlorination, provides a one-pot synthesis of [Ru(pyS),(CO),J in high yield (89%). Earlier we had prepared this dicarbonyl from [Ru~(CO),~] with an excess of ~YSH.~ Initially the reaction of pySH with [Ru~(CO),~] gives the trinuclear compound [Ru,H(p-pyS)(CO),], but this reacts easily with an excess of pySH to give the mononuclear compound. This is a satisfactory synthesis but more expensive than that from RuCl, - 3H20 and is less convenient even though the yields are good in both cases. The compound [Ru(pyS),(CO)d was obtained as yellow, air-stable crystals which were simply characterized by IR and NMR spectra (Table 1). It is closely related to the corresponding osmium com-
837
838
A. J. DEEMING
and M. KARIM
Table 1. Selected spectroscopic data for the new compounds Compound
v(CQY (cm-‘)
DWPYWW,I
2046~s 1988s
1934vs
[Ru(Mepy%(CQl
2048s 1987s
[Ru(quin%(C%l
2051s 1991s
[RuC&(quinSH),(CO),]
2061s 1998s
[R&1,(4,8-Me,quinSH),(C0),1
2055s 1988s
‘H NMRh 8.13(ddd,H6) 7.38(ddd,H4) 6.86(ddd,H3) 6.75(ddd,H5) 13.3(s,br,NH) 8.30(ddd,H6,pyS) 8. 12(ddd,H6,pyS) 7.63(ddd,H3,pySH) 7.60(d,br,H6,pySH) 7.28(m,3H4) 6.88(ddd,H3,pyS) 6.84(ddd,H3,pyS) 6.6-6.8(m,3H5) 7.23&H’) 6.68(d,H3) 6.50(d,H5) 2.62(s,Me) 8.85(d,H8) 7.66(d,H4) 7.53(m,H5,H6) 7.26(m,H7) 6.29(d,H3) 14.5(s,br,NH) 7.75(d,H8) 7.55-7.65(m,H&) 7.28-7.40(m,H3,H7) 13.3(s,br,NH) 7.65(d,H6) 7.45(m,HS,H7) 7.25(m,H3) 2.91(s,Me) 2.58(s,Me)
J35 1.3 J34 8.3 J46 1.3 Jd5 7.9 Js6 5.5 J 0.9, 1.8, 5.4 J0.9, 1.7, 5.5
J8.0
J 8.0 58.8
58.8 J 9.0
J 7.2
“In cyclohexane except for dichloro compounds which were in dichloromethane. ‘In CDCl, at 200 MHz.
pound, which we have synthesized indirectly from [OS~(CO),~].’ The reaction of trifluoroactic acid with the dodecacarbonyl gives [Os(CF,CO,),(CO),] and this can be converted with pySH into [O~(pys)~ (CO),], which has been structurally characterized by XRD. The pyS ligands are equivalent, the carbony1 cis and the S-atoms tram, and the ruthenium compound is almost certainly isostructural with it. The minor product analyses as [Ru(pySX (pySH)(CO)] and contains non-equivalent chelating pyS ligands and a S-bonded pySH thione ligand (‘H NMR evidence, Table 1). The NH proton in the ‘H NMR spectrum appears as a broad singlet at 6 13.3. We cannot be sure of the structure based on spectra but simple carbonyl substitution without rearrangement is likely since the compound
would then have a structure related to those established for [Ru(pyS),(CO)(PPh# and [Ru(pyS),
W’Wh9 Directly comparable reactions of RuC13 * 3H20 with other thiones have been examined : 6-methylpyridine-2-thione (MepySH), quinoline-Zthione (quinSH) and 4,8-dimethylquinoline-2-thione (4,8MequinSH). The only product from MepySH is [Ru(MepyS),(CO),], which is directly analogous to the parent pyS compound but is formed in much lower yield. We have not accounted for the different yield but most of the material from the reaction does not elute on the TLC plate and we have been unable to characterize it. The other two thiones give good yields but mainly of the chloro complexes [RuC~~(CO)~L~] (L = quinSH or 4,8-MeZquinSH),
Mononuclear pyridine-Zthionato complexes RuCl3.3H20 -
co ROH
IRuC13iC0~31ZPYSH I
-HCI
was separated by TLC [SiOZ; light petroleum (b.p. <40”C)-dichloromethane (1 : 1 v/v)] to give one main yellow band yielding [Ru(~~S),(CO)~] as yellow crystals (0.129 g, 89%) from a dichloromethane and hexane mixture (Found: C, 38.1, H, 2.0; N, 7.25; S, 16.75. Ci2HBN202RuS2 requires: C, 38.2; H, 2.15 ; N, 7.4 ; S, 17.0%). A minor band yielded a monocarbonyl species as an orange solid, shown by its spectra to be [Ru(pyS),(pySH)(CO)] (0.006 g, 3%) (see alternative synthesis below).
Reaction of [Ru3(CO),J 2-thione
-HCI
Scheme 1.
which correspond to the products expected from neutral ligands. The ligand quinSH also gives a minor amount of the dehydrochlorination product [Ru(quinS),(CO),]. We propose the reaction route given in Scheme 1. The initial reaction leads to the adducts [RuC~~(CO)~L~]which are isolable for the more sterically demanding thiones and the only product for 4,8-MequinSH. Deprotonation of these thione complexes would give thionato species but it would seem that the thionato ligands, quinS and 4,8-Me,quinS, do not easily form chelate rings with the displacement of a c&chloride ligand. Certainly with 4,8-Me,quinS there would be a serious clash of the g-methyl group with an adjacent cis ligand if a chelate ring were formed. When chelate ring formation creates no such problem, it occurs readily as in the formation of [Ru(pyS),(CO),] and in this case the chloro species are not observed. EXPERIMENTAL Reaction of RuCl, * 3H,O with carbon monoxide followed by pyridine-Zthione
Carbon monoxide gas was bubbled through a refluxing dark red-brown solution of ruthenium trichloride (0.100 g, 0.38 mmol) in 2-methoxyethanol (40 cm3) for 3 h to give a yellow solution. Pyridine-Zthione (0.106 g, 0.95 mmol) was added and the reflux without carbon monoxide gas was continued for 2 h. Water was added and the mixture extracted with dichloromethane. The dichloromethane was removed to give a yellow oil which
839
with an excess ofpyridine-
A solution of [Ru~(CO),~] (0.200 g, 0.31 mmol) and pySH (0.208 g, 1.19 mmol) in m-xylene was refluxed under nitrogen for 2 h. The deep yellow residue after removal of the solvent in uacuo was separated by TLC [SiOZ: light petroleum (b.p. <40”C)-dichloromethane (1 : 1 v/v)]. The major band gave [Ru(pyS),(CO),] as yellow crystals (0.3 17 g, 89%) (Found : C, 38.1; H, 2.25 ; N, 7.35 ; S, 16.75%) and a minor band gave [Ru(pyS), (pySH)(CO)] as orange needles (0.008 g, 2%) from a dichloromethane-hexane mixture (Found : C, 41.25; H, 2.8; N, 8.9; S, 20.85. C,6H,3N30R~S3 requires: C, 41.7; H, 2.85; N, 9.1 ; S, 20.9%). Both were spectroscopically identical to the products from the previous synthesis.
Reaction of R&l, * 3H20 with carbon monoxide followed by 6-methylpyridine-Zthione
Carbon monoxide was bubbled through a refluxing solution of ruthenium trichloride (0.200 g, 0.76 mmol) in 2-methoxyethanol (40 cm3) for 3 h. The bubbling was stopped, MepySH (0.239 g, 1.90 mmol) was added and the solution refluxed for 2 h. TLC work-up as above gave [Ru(MepyS),(CO)z] as yellow crystals (0.0207 g, 7%) (Found : C, 41.2; H, 2.85 ; N, 6.7 ; S, 15.1. Cr4H,,N,0,RuS, requires : C, 41.45; H, 3.0; N, 6.9; S, 15.8%). There were other low-yield and uncharacterized products but most of the material did not elute and was not studied further.
Reaction of RuCl, * 3H20 with carbon monoxide followed by quinoline-2-thione
Carbon monoxide was bubbled through a refluxing solution of ruthenium trichloride (0.300 g, 1.15 mmol) in 2-methoxyethanol(40 cm3) for 3 h. Quinoline-Zthione (0.462 g, 2.87 mmol) was added and the solution refluxed for 15 min. Brick-red crystals,
840
A. J. DEEMING
which deposited on cooling for 1 h, were collected, washed with light petroleum (b.p. ~40°C) and characterized as [RuC12(quinSH)2(C0)2] (0.595 g, 94%) (Found: C, 43.65; H, 2.7; Cl, 12.8; N, 4.95; S, 11.25. C20H,4N202C12R~S2requires : C, 43.65 ; H, 2.55; Cl, 12.9; N, 5.1 ; S, 11.65%). Removal of the solvent from the mother liquor and TLC of the residue [SiOZ; light petroleum (b.p. <4O”C)methanol (19 : 1 v/v)] gave [Ru(quinS),(CO),] as yellow crystals (0.010 g, 2%) from a dichloromethane methanol mixture (Found : C, 49.45 ; H, 2.45 ; N, 5.5. C20H12N202R~S2requires : C, 50.3 ; H, 2.55 ; N, 5.85%).
Reaction of RuCI, * 3H20 with carbon followed by 4,8-dimethylquinoline-2-thione
monoxide
Treatment of ruthenium trichloride (0.200 g, 0.76 mmol) in 2-methoxyethanol (40 cm3) with carbon monoxide as above, followed by treatment with the thione (0.285 g, 1.51 mmol) and further reflux for 2 h gave a solution which deposited brick-red crystals (0.272 g) on cooling for 1 h. Removal of the solvent from the mother liquor and recrystallization of the residue from a dichloromethane-methanol mixture gave more brick-red crystals (0.125 g). The total yield of [RuC1,(4,8-Me,quinSH),(CO),] was 0.342 g(74%)(Found:C,47.2;H,3.65;C1,11.5;N,4.6; S, 10.5. C24H22C12N202R~S2requires: C, 47.5; H, 3.65; Cl, 11.4; N, 4.6; S, 10.5%).
and M. KARIM
Acknowledgements-We thank the Association of Commonwealth Universities for a studentship (for M.K.) and Johnson-Matthey for a loan of RuCI~ * 3H,O.
REFERENCES B. L. Shaw and A. E. Field, J. Chem. Sot. 1964, 3466; M. L. Berth and A. Davison, J. Inorg. Nucl. Chem. 1973,35,3763. 2. W. Manchot and J. K&rig, Berichte 1924, 57, 2130 ; A. T. Stephenson and G. Wilkinson, J. Inorg. Nucl. 1. J. Chatt,
Chem. 1966, 28, 945; J. V. Kingston and G. R. Scollary, J. Inorg. Nucl. Chem. 1972, 34, 227; J. P. Collman and W. R. Roper, J. Am. Chem. Sot. 1965, 87,4008 ; J. M. Jenkins, M. S. Lupin and B. L. Shaw, J. Chem. Sot. A 1966, 1787 ; M. S. Lupin and B. L. Shaw, J. Chem. Sot. A 1968, 741; D. F. Gill, B. E. Mann and B. L. Shaw, J. Chem. Sot., Dalton Trans.
1973,311. 3. B. Cockerton, A. J. Deeming, K. I. Hardcastle and M. Karim, unpublished results. 4. A. J. Deeming and M. Karim, unpublished results. 5. P. Mura, B. G. Olby and S. D. Robinson, J. Chem.
Sot., Dalton Trans. 1985, 2101. 6. N. Ahmed, S. D. Robinson
and M. F. Uttley, J. Chem. Sot., Dalton Trans. 1972, 843. 7. N. Ahmed, S. D. Robinson, J. J. Levison and M. F. Uttley, Inorg. Chem. 1975, 15,45. 8. A. J. Deeming, M. N. Meah, N. P. Randle and K. I. Hardcastle, J. Chem. Sot., Dalton Trans. 1989, 2211. 9. S. R. Fletcher and A. C. Skapski, J. Chem. Sot.,
Dalton Trans. 1972, 635.
0
0277-5387/91 %3.00+.00 1991 Pergamon Press plc
MONONUCLEAR PYRIDINE-2-THIONA’ COMPLEXES FORMED DIRECTLY FROM RUTHENIUM TRICHLORIDE ANTONY J. DEEMING* and MANZURUL KARIM Department of Chemistry, University College London, 20 Gordon Street, London WClH OAJ, U.K. (Received 21 August 1990 ; accepted 4 January 1991)
Abstract-Reductive carbonylation of ruthenium trichloride in refluxing 2-methoxyethanol leads to a chlorocarbonyl complex of ruthenium(I1) which reacts directly with pyridine-2thione (pySH) to give high yields of [Ru(pyS),(CO),], and the 6-methylpyridine-2-thionato analogue is prepared similarly but in much lower yield. Quinoline-2-thione (quinSH) gives high yields of the compound [RuCl,(quinSH),(CO),] and only low yields of the dehydrochlorination compound [Ru(quinS),(CO),]. The more crowded thione, 4,8-dimethylquinoline-Zthione, gives only the chloro complexes and no dehydrochlorination.
Ruthenium(I1) chlorocarbonyl complexes are easily synthesized by treating ruthenium trichloride with carbon monoxide in refluxing alcoholic solvents, followed by the addition of a neutral ligand.’ For example, tertiary phosphine complexes such as [RuCl,(CO),L,] are readily synthesized in this way.‘,’ We wished to synthesize mononuclear pyridine-2-thionato complexes of ruthenium as starting materials for the synthesis of cluster and cage compounds, for example, we have synthesized the 2-pyridyl clusters [Ru,(S),(C,H,N),(CO), ,] and [Rus(S)&H~N)l(CO),,l from [Ru(pyS)z(CO),l and [Ru,(CO),,],~ and these results will be reported later. We originally synthesized [Ru(pyS),(CO),] from [Ru~(CO),~] and an excess of pySH under vigorous conditions4 but we sought a good easy route from RuCl, * 3H,O and this method is described herein. RESULTS AND DISCUSSION It is well known that bubbling carbon monoxide through a refluxing solution of ruthenium trichloride in 2-methoxyethanol gives a yellow solution containing reactive ruthenium(I1) chlorocarbony1 species.’ Probably the major one present is ,fac-[RuCl,(CO),]-. These solutions are valuable in the synthesis of ruthenium(I1) species and tertiary phosphines, arsines, amines, pyridine (L), etc., give
*Author to whom correspondence
should be addressed.
[RuC~~(CO)~L~] or [RuC12(CO)L3] in different stereochemistries.‘,* Ruthenium(I1) pyridine-2-thione (pySH) or thionato (pyS) complexes have been prepared previously from tertiary phosphine-containing precursors and all contain tertiary phosphines, e.g. [Ru(pyS),(CO)(PPh,)l, [RuH(pyS)(CO)(PPh,),, [Ru (pyS),(CO),(PPh,)l, [RuHCl(pySH)(CO)(PPh,)1, or [RuCl(pyS)(pySH)(CO)(PPh3)2].~7 These complexes contain pyS as a monodentate S-bonded or chelating ligand or pySH as a S-bonded neutral thione ligand. In looking for a straightforward route to [Ru (‘pyS),(CO),] from RuCl, - 3H20, we found that treatment of the 2-methoxyethanol solution containing ruthenium(I1) chlorocarbonyl species with pySH, followed by thermal dehydrochlorination, provides a one-pot synthesis of [Ru(pyS),(CO),J in high yield (89%). Earlier we had prepared this dicarbonyl from [Ru~(CO),~] with an excess of ~YSH.~ Initially the reaction of pySH with [Ru~(CO),~] gives the trinuclear compound [Ru,H(p-pyS)(CO),], but this reacts easily with an excess of pySH to give the mononuclear compound. This is a satisfactory synthesis but more expensive than that from RuCl, - 3H20 and is less convenient even though the yields are good in both cases. The compound [Ru(pyS),(CO)d was obtained as yellow, air-stable crystals which were simply characterized by IR and NMR spectra (Table 1). It is closely related to the corresponding osmium com-
837
838
A. J. DEEMING
and M. KARIM
Table 1. Selected spectroscopic data for the new compounds Compound
v(CQY (cm-‘)
DWPYWW,I
2046~s 1988s
1934vs
[Ru(Mepy%(CQl
2048s 1987s
[Ru(quin%(C%l
2051s 1991s
[RuC&(quinSH),(CO),]
2061s 1998s
[R&1,(4,8-Me,quinSH),(C0),1
2055s 1988s
‘H NMRh 8.13(ddd,H6) 7.38(ddd,H4) 6.86(ddd,H3) 6.75(ddd,H5) 13.3(s,br,NH) 8.30(ddd,H6,pyS) 8. 12(ddd,H6,pyS) 7.63(ddd,H3,pySH) 7.60(d,br,H6,pySH) 7.28(m,3H4) 6.88(ddd,H3,pyS) 6.84(ddd,H3,pyS) 6.6-6.8(m,3H5) 7.23&H’) 6.68(d,H3) 6.50(d,H5) 2.62(s,Me) 8.85(d,H8) 7.66(d,H4) 7.53(m,H5,H6) 7.26(m,H7) 6.29(d,H3) 14.5(s,br,NH) 7.75(d,H8) 7.55-7.65(m,H&) 7.28-7.40(m,H3,H7) 13.3(s,br,NH) 7.65(d,H6) 7.45(m,HS,H7) 7.25(m,H3) 2.91(s,Me) 2.58(s,Me)
J35 1.3 J34 8.3 J46 1.3 Jd5 7.9 Js6 5.5 J 0.9, 1.8, 5.4 J0.9, 1.7, 5.5
J8.0
J 8.0 58.8
58.8 J 9.0
J 7.2
“In cyclohexane except for dichloro compounds which were in dichloromethane. ‘In CDCl, at 200 MHz.
pound, which we have synthesized indirectly from [OS~(CO),~].’ The reaction of trifluoroactic acid with the dodecacarbonyl gives [Os(CF,CO,),(CO),] and this can be converted with pySH into [O~(pys)~ (CO),], which has been structurally characterized by XRD. The pyS ligands are equivalent, the carbony1 cis and the S-atoms tram, and the ruthenium compound is almost certainly isostructural with it. The minor product analyses as [Ru(pySX (pySH)(CO)] and contains non-equivalent chelating pyS ligands and a S-bonded pySH thione ligand (‘H NMR evidence, Table 1). The NH proton in the ‘H NMR spectrum appears as a broad singlet at 6 13.3. We cannot be sure of the structure based on spectra but simple carbonyl substitution without rearrangement is likely since the compound
would then have a structure related to those established for [Ru(pyS),(CO)(PPh# and [Ru(pyS),
W’Wh9 Directly comparable reactions of RuC13 * 3H20 with other thiones have been examined : 6-methylpyridine-2-thione (MepySH), quinoline-Zthione (quinSH) and 4,8-dimethylquinoline-2-thione (4,8MequinSH). The only product from MepySH is [Ru(MepyS),(CO),], which is directly analogous to the parent pyS compound but is formed in much lower yield. We have not accounted for the different yield but most of the material from the reaction does not elute on the TLC plate and we have been unable to characterize it. The other two thiones give good yields but mainly of the chloro complexes [RuC~~(CO)~L~] (L = quinSH or 4,8-MeZquinSH),
Mononuclear pyridine-Zthionato complexes RuCl3.3H20 -
co ROH
IRuC13iC0~31ZPYSH I
-HCI
was separated by TLC [SiOZ; light petroleum (b.p. <40”C)-dichloromethane (1 : 1 v/v)] to give one main yellow band yielding [Ru(~~S),(CO)~] as yellow crystals (0.129 g, 89%) from a dichloromethane and hexane mixture (Found: C, 38.1, H, 2.0; N, 7.25; S, 16.75. Ci2HBN202RuS2 requires: C, 38.2; H, 2.15 ; N, 7.4 ; S, 17.0%). A minor band yielded a monocarbonyl species as an orange solid, shown by its spectra to be [Ru(pyS),(pySH)(CO)] (0.006 g, 3%) (see alternative synthesis below).
Reaction of [Ru3(CO),J 2-thione
-HCI
Scheme 1.
which correspond to the products expected from neutral ligands. The ligand quinSH also gives a minor amount of the dehydrochlorination product [Ru(quinS),(CO),]. We propose the reaction route given in Scheme 1. The initial reaction leads to the adducts [RuC~~(CO)~L~]which are isolable for the more sterically demanding thiones and the only product for 4,8-MequinSH. Deprotonation of these thione complexes would give thionato species but it would seem that the thionato ligands, quinS and 4,8-Me,quinS, do not easily form chelate rings with the displacement of a c&chloride ligand. Certainly with 4,8-Me,quinS there would be a serious clash of the g-methyl group with an adjacent cis ligand if a chelate ring were formed. When chelate ring formation creates no such problem, it occurs readily as in the formation of [Ru(pyS),(CO),] and in this case the chloro species are not observed. EXPERIMENTAL Reaction of RuCl, * 3H,O with carbon monoxide followed by pyridine-Zthione
Carbon monoxide gas was bubbled through a refluxing dark red-brown solution of ruthenium trichloride (0.100 g, 0.38 mmol) in 2-methoxyethanol (40 cm3) for 3 h to give a yellow solution. Pyridine-Zthione (0.106 g, 0.95 mmol) was added and the reflux without carbon monoxide gas was continued for 2 h. Water was added and the mixture extracted with dichloromethane. The dichloromethane was removed to give a yellow oil which
839
with an excess ofpyridine-
A solution of [Ru~(CO),~] (0.200 g, 0.31 mmol) and pySH (0.208 g, 1.19 mmol) in m-xylene was refluxed under nitrogen for 2 h. The deep yellow residue after removal of the solvent in uacuo was separated by TLC [SiOZ: light petroleum (b.p. <40”C)-dichloromethane (1 : 1 v/v)]. The major band gave [Ru(pyS),(CO),] as yellow crystals (0.3 17 g, 89%) (Found : C, 38.1; H, 2.25 ; N, 7.35 ; S, 16.75%) and a minor band gave [Ru(pyS), (pySH)(CO)] as orange needles (0.008 g, 2%) from a dichloromethane-hexane mixture (Found : C, 41.25; H, 2.8; N, 8.9; S, 20.85. C,6H,3N30R~S3 requires: C, 41.7; H, 2.85; N, 9.1 ; S, 20.9%). Both were spectroscopically identical to the products from the previous synthesis.
Reaction of R&l, * 3H20 with carbon monoxide followed by 6-methylpyridine-Zthione
Carbon monoxide was bubbled through a refluxing solution of ruthenium trichloride (0.200 g, 0.76 mmol) in 2-methoxyethanol (40 cm3) for 3 h. The bubbling was stopped, MepySH (0.239 g, 1.90 mmol) was added and the solution refluxed for 2 h. TLC work-up as above gave [Ru(MepyS),(CO)z] as yellow crystals (0.0207 g, 7%) (Found : C, 41.2; H, 2.85 ; N, 6.7 ; S, 15.1. Cr4H,,N,0,RuS, requires : C, 41.45; H, 3.0; N, 6.9; S, 15.8%). There were other low-yield and uncharacterized products but most of the material did not elute and was not studied further.
Reaction of RuCl, * 3H20 with carbon monoxide followed by quinoline-2-thione
Carbon monoxide was bubbled through a refluxing solution of ruthenium trichloride (0.300 g, 1.15 mmol) in 2-methoxyethanol(40 cm3) for 3 h. Quinoline-Zthione (0.462 g, 2.87 mmol) was added and the solution refluxed for 15 min. Brick-red crystals,
840
A. J. DEEMING
which deposited on cooling for 1 h, were collected, washed with light petroleum (b.p. ~40°C) and characterized as [RuC12(quinSH)2(C0)2] (0.595 g, 94%) (Found: C, 43.65; H, 2.7; Cl, 12.8; N, 4.95; S, 11.25. C20H,4N202C12R~S2requires : C, 43.65 ; H, 2.55; Cl, 12.9; N, 5.1 ; S, 11.65%). Removal of the solvent from the mother liquor and TLC of the residue [SiOZ; light petroleum (b.p. <4O”C)methanol (19 : 1 v/v)] gave [Ru(quinS),(CO),] as yellow crystals (0.010 g, 2%) from a dichloromethane methanol mixture (Found : C, 49.45 ; H, 2.45 ; N, 5.5. C20H12N202R~S2requires : C, 50.3 ; H, 2.55 ; N, 5.85%).
Reaction of RuCI, * 3H20 with carbon followed by 4,8-dimethylquinoline-2-thione
monoxide
Treatment of ruthenium trichloride (0.200 g, 0.76 mmol) in 2-methoxyethanol (40 cm3) with carbon monoxide as above, followed by treatment with the thione (0.285 g, 1.51 mmol) and further reflux for 2 h gave a solution which deposited brick-red crystals (0.272 g) on cooling for 1 h. Removal of the solvent from the mother liquor and recrystallization of the residue from a dichloromethane-methanol mixture gave more brick-red crystals (0.125 g). The total yield of [RuC1,(4,8-Me,quinSH),(CO),] was 0.342 g(74%)(Found:C,47.2;H,3.65;C1,11.5;N,4.6; S, 10.5. C24H22C12N202R~S2requires: C, 47.5; H, 3.65; Cl, 11.4; N, 4.6; S, 10.5%).
and M. KARIM
Acknowledgements-We thank the Association of Commonwealth Universities for a studentship (for M.K.) and Johnson-Matthey for a loan of RuCI~ * 3H,O.
REFERENCES B. L. Shaw and A. E. Field, J. Chem. Sot. 1964, 3466; M. L. Berth and A. Davison, J. Inorg. Nucl. Chem. 1973,35,3763. 2. W. Manchot and J. K&rig, Berichte 1924, 57, 2130 ; A. T. Stephenson and G. Wilkinson, J. Inorg. Nucl. 1. J. Chatt,
Chem. 1966, 28, 945; J. V. Kingston and G. R. Scollary, J. Inorg. Nucl. Chem. 1972, 34, 227; J. P. Collman and W. R. Roper, J. Am. Chem. Sot. 1965, 87,4008 ; J. M. Jenkins, M. S. Lupin and B. L. Shaw, J. Chem. Sot. A 1966, 1787 ; M. S. Lupin and B. L. Shaw, J. Chem. Sot. A 1968, 741; D. F. Gill, B. E. Mann and B. L. Shaw, J. Chem. Sot., Dalton Trans.
1973,311. 3. B. Cockerton, A. J. Deeming, K. I. Hardcastle and M. Karim, unpublished results. 4. A. J. Deeming and M. Karim, unpublished results. 5. P. Mura, B. G. Olby and S. D. Robinson, J. Chem.
Sot., Dalton Trans. 1985, 2101. 6. N. Ahmed, S. D. Robinson
and M. F. Uttley, J. Chem. Sot., Dalton Trans. 1972, 843. 7. N. Ahmed, S. D. Robinson, J. J. Levison and M. F. Uttley, Inorg. Chem. 1975, 15,45. 8. A. J. Deeming, M. N. Meah, N. P. Randle and K. I. Hardcastle, J. Chem. Sot., Dalton Trans. 1989, 2211. 9. S. R. Fletcher and A. C. Skapski, J. Chem. Sot.,
Dalton Trans. 1972, 635.