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Some reactions of M(SC6Cl5)2, M = Ni, Pd, Pt
3267
Notes J. inorg, nuel. Chem., 1972, Vol. 34, pp. 3267-3268.
Pergamon Press.
Printed in Great Britain
Some reactions of M(SC6Cls)2, M = Ni, Pd, Pt (Received 10 January 1972)
TRANSITION metals are known to form polymeric thiolates with sulphur bridges [ 1]. The tendency to form polymers is reduced when an electron withdrawing thiol, such as pentafluorothiophenol is used, and the platinum(If) and palladium(II) compounds, M(SC~Fs)._,, form complexes of the type, [M(SC,F5)4]2- and M(SC~Fs)z(PPh3)2, and [Pd(Ph3P)(SCrFs)2]2[2, 3]. In the latter compound the ligands are approximately square planar about each palladium, with two sulphur bridges and the non-bridging CrF~S ligands trans [4]. The CrFsS groups are also trans in the approximate square planar compound (Bu3P)zPd(SCrFs)2 [5]. Derivatives of pentachlorothiophenol should be analogous to those of pentafluorothiophenol, if the CrCI~ group is also electron withdrawing. The compound Pd(SCsCIs)2 has been prepared[6] and shown to form the complex ion [Pd(SCrC15)4] 2- which may be stabilized as its tetraphenylarsonium and potassium salts. Attempts to stabilize this ion as the tetrabutylammonium salt failed. The formation of complexes of the type Pd(SCrCIs)2L2 has been studied with various ligands. Reddish brown Pd(SCrCIs)2 is somewhat soluble in pyridine(py) and ethylenediamine(en), more so than in D M F or DMSO and virtually insoluble in MeOH, EtOH, Me2CO, CHCI3, CH2C12, CICH~CH2C1, MeCN. C~H6 and HzO. Ethylene diamine in ethanol did not react with a suspension of Pd(SCrC15h but when it was refluxed with pure ethylene diamine a reddish brown product of empirical formula about PdCsHIrN4C13S0.38 was isolated. The pyridine complex Pd(SCrCIs)2Py2 was obtained by refluxing a suspension of Pd(SCrC15)z in pyridine. No complexes could be formed with excess triphenyl phosphine and a suspension of the thiolate in alcohol but when ethylene bisdiphenylphosphine (EDP) was used, a complex Pd(SrCIs)2 (EDP) was isolated. It can be concluded that the Pd-S bond is relatively readily fractured in Pd(SCnCI~)~ and that both pentafluoro- and pentachloro-thiophenol have similar electronic effects on palladium in their polymers. The formation of the complex ions [M(SCrCI~)4]-'- where M = Ni, Pt, further indicates the relative lability of the M - S bond in this group. EXPERIMENTAL Bis(pentachlorothiophenolate) palladium(II), Pd(SCrCIs)2, has been prepared previously from shaking a benzene solution of the thiol with an aqueous HCI solution of palladium(If) chloride[6] or it can be prepared from palladium(II) acetate and pentachlorothiophenol in methanol. Reaction with pyridine. A suspension of Pd(SCrCIs)2 (1.34 g) in 50 ml of Py was refluxed for 72 hr. After removing the unreacted Pd(SC~CI~)2, the solution was concentrated to a small volume and small crystals of Pd(SCrCIs)2Py2 separated. These were filtered off and washed once with Py followed by ether. The product was dried in vacuo over sodium hydroxide. Yield 0.30 g. Anal. Calcd. for C~2H~oCI10N2S2Pd: C, 31.90; H, 1.22; N, 3-38. Found: C, 32.59; H, 1.46; N, 3.29. Reaction with ethylenediamine. A suspension of Pd(SCrCIs)2 (1.34 g) in 25 ml of en was refluxed for 24 hr and filtered. The filtrate was concentrated and on addition of methanol (15 ml) a black product separated on standing. The product was filtered off, washed with small amounts of MeOH and dried in vacuo over NaOH. Yield 0-41 g. Analysis indicated considerable loss of sulphur from the Pd(SCrCI~)2 and that the product had empirical formula of about PdCrH~rN4C13S0.36. 1. S. E. Livingston, Quart. Rev. 386 (1965). 2. W. Beck, K. H. Stetter, S. Tadros and K. E. Schwazhans, Chem. Ber. 100, 3944 (1967). 3. R. S. Nyholm, J. F. Skinner and M. H. B. Stiddard, J. chem. Soc. (A) 38 (1968); R. S. Nyholm and B. R. Hollebone, J. chem. Soc. (A) 332 (1971). 4. R. H. Fenn and G. R. Segrott, J. chem. Soc. (A) 3197 (1970). 5. R. H. Fenn and G. R. Segrott, J. chem. Soc. (A) 278 (1970). 6. C. R. Lucas and M. E. Peach, lnorg, nucl. Chem. Lett. 5, 73 (1969): Can. J. Chem. 48, 1869 (1970).
3268
Notes
Reaction with triphenylphosphine. An ethanol solution of Ph3P (5"25 g in 124 ml) containing 1.34 g of Pd(SCeCID2 was refluxed for 4 d. The brown mixture was poured into 250 ml of EtOH and filtered after boiling for 15 min. The brown insoluble product (1-08 g) was shown by its i.r. spectrum to be Pd(SCnCID2. Evaporation of the solvent from the filtrate left Ph3P (found M.P. 80°; lit. M.P. 80°). .Reaction with ethylene-bis(diphenyl phosphine). Pd(SC6CIs)2 (1.34g) was added to an ethanol solution of EDP (1 '59 g in 200 ml) and the mixture refluxed for 72 hr. The yellow product was filtered off, washed with EtOH and Et20 and air dried. Yield, 2"0 g. Anal. Calcd. for C3sH24CIloP2S2Pd: C, 42"78; H, 2.27; S, 6.01. Found: C, 42"84; H, 2.40; S, 5.98. The product is soluble in MeOH, EtOH, CHCI3, CH2C12, C1CH~CHzC1, C6Hr, Py, DMF, DMSO and Me.2CO. Complex ions A solution of PdCI2 (0.0925 g in 20 ml H20 + one drop HCI) was added to an aqueous solution of CrCIsSH (0.561 g in 20 ml H20 with sufficient N a O H to achieve solution). This solution was filtered and added to a solution of Ph4AsC1 (0.420 g in 10 ml HeO): the red brown precipitate was filtered off after an hour and washed with water. Yield 0.667 g. M.P. 242°d. Anal. Calcd. for C72H40As2C120PdS4: C, 43.27; H, 2.02; Pd, 5.32. Found: C, 42.99; H, 2.05; Pd, 5.46. The product was soluble in Me2CO, insoluble in EtOH, Et20, CrHr, and pet. ether. The compound (PI~As)2[Ni(SCrCI5)4] was prepared similarly starting from Ni(NO3)z.6H20 (0.145g). Yield 0.429g. Anal. Calcd. for Cr2H4oAs2C120NiS4: C, 44.33; H, 2.07; Ni, 3.01. Found: C, 44.56; H, 2'58; Ni, 3'31. The potassium salt K2[Pd(SCnCIs)4] was prepared by adding an alkaline solution of CeCIsSH (1.13 g in 5 ml) to K2PdCI4 (0"33 g in 20 ml H20). The dark red product separated immediately, which, after standing, was filtered off, washed with H20, EtOH, and Et20, then air dried. Yield 0.98 g. Anal. Calcd. for C24C120K2PdS4: C, 22.54; H, 0.00; S, 10.04. Found: C, 22.70; H, 0.64; S, 9"18. Attempts to isolate a pure Bu4N + salt from an analogous reaction by adding an alkaline solution of CeCIsSH to a solution of Bu4NBr and K2PdCI4 failed. The compound Kz[Pt(SCrCIs)4] was prepared analogously, starting from K2PtCI4 (0"214 g). Yield 0.642 g. Anal. Calcd. for C24CI2oK2PtS4: C, 20.61 ; H, 0.0; S, 9.17. Found: C, 21.05; H, 0.3; S, 9-03.
Acknowledgement-The financial assistance of the National Research Council of Canada for an operating grant and a studentship (C.R.L.) is gratefully acknowledged.
Department of Chemistry Acadia University Wolfville Nova Scotia Canada
C. R. LUCAS* M. E. P E A C H K. K. R A M A S W A M Y t
* Present address: Inorganic Chemistry Laboratory, Oxford University, England. tPresent address: Humphrey Chemical Company, New Haven, Conn. 06473, U.S.A.
J. inorg, nucl. Chem., 1972, Vol. 34, pp. 3268-327 I.
Pergamon Press.
Printed in Great Britain
The crystal structure of a S r U O 4.000 (Received 24 January 1972) DURING a study of the phase systems MO-UO2-O2 (M = Ba, Sr, Ca and Cd), a monophasic sample of c~ SrUO4.ooo was prepared and characterized by X-ray and chemical analyses. The sample, yellow in colour had a mole composition of SrO/UO~.oo~ _+o.ooz= 0.998 and X-ray examination using the HaggGuinier camera showed the absence of any of the strong reflections to be expected from the phases
Notes J. inorg, nuel. Chem., 1972, Vol. 34, pp. 3267-3268.
Pergamon Press.
Printed in Great Britain
Some reactions of M(SC6Cls)2, M = Ni, Pd, Pt (Received 10 January 1972)
TRANSITION metals are known to form polymeric thiolates with sulphur bridges [ 1]. The tendency to form polymers is reduced when an electron withdrawing thiol, such as pentafluorothiophenol is used, and the platinum(If) and palladium(II) compounds, M(SC~Fs)._,, form complexes of the type, [M(SC,F5)4]2- and M(SC~Fs)z(PPh3)2, and [Pd(Ph3P)(SCrFs)2]2[2, 3]. In the latter compound the ligands are approximately square planar about each palladium, with two sulphur bridges and the non-bridging CrF~S ligands trans [4]. The CrFsS groups are also trans in the approximate square planar compound (Bu3P)zPd(SCrFs)2 [5]. Derivatives of pentachlorothiophenol should be analogous to those of pentafluorothiophenol, if the CrCI~ group is also electron withdrawing. The compound Pd(SCsCIs)2 has been prepared[6] and shown to form the complex ion [Pd(SCrC15)4] 2- which may be stabilized as its tetraphenylarsonium and potassium salts. Attempts to stabilize this ion as the tetrabutylammonium salt failed. The formation of complexes of the type Pd(SCrCIs)2L2 has been studied with various ligands. Reddish brown Pd(SCrCIs)2 is somewhat soluble in pyridine(py) and ethylenediamine(en), more so than in D M F or DMSO and virtually insoluble in MeOH, EtOH, Me2CO, CHCI3, CH2C12, CICH~CH2C1, MeCN. C~H6 and HzO. Ethylene diamine in ethanol did not react with a suspension of Pd(SCrC15h but when it was refluxed with pure ethylene diamine a reddish brown product of empirical formula about PdCsHIrN4C13S0.38 was isolated. The pyridine complex Pd(SCrCIs)2Py2 was obtained by refluxing a suspension of Pd(SCrC15)z in pyridine. No complexes could be formed with excess triphenyl phosphine and a suspension of the thiolate in alcohol but when ethylene bisdiphenylphosphine (EDP) was used, a complex Pd(SrCIs)2 (EDP) was isolated. It can be concluded that the Pd-S bond is relatively readily fractured in Pd(SCnCI~)~ and that both pentafluoro- and pentachloro-thiophenol have similar electronic effects on palladium in their polymers. The formation of the complex ions [M(SCrCI~)4]-'- where M = Ni, Pt, further indicates the relative lability of the M - S bond in this group. EXPERIMENTAL Bis(pentachlorothiophenolate) palladium(II), Pd(SCrCIs)2, has been prepared previously from shaking a benzene solution of the thiol with an aqueous HCI solution of palladium(If) chloride[6] or it can be prepared from palladium(II) acetate and pentachlorothiophenol in methanol. Reaction with pyridine. A suspension of Pd(SCrCIs)2 (1.34 g) in 50 ml of Py was refluxed for 72 hr. After removing the unreacted Pd(SC~CI~)2, the solution was concentrated to a small volume and small crystals of Pd(SCrCIs)2Py2 separated. These were filtered off and washed once with Py followed by ether. The product was dried in vacuo over sodium hydroxide. Yield 0.30 g. Anal. Calcd. for C~2H~oCI10N2S2Pd: C, 31.90; H, 1.22; N, 3-38. Found: C, 32.59; H, 1.46; N, 3.29. Reaction with ethylenediamine. A suspension of Pd(SCrCIs)2 (1.34 g) in 25 ml of en was refluxed for 24 hr and filtered. The filtrate was concentrated and on addition of methanol (15 ml) a black product separated on standing. The product was filtered off, washed with small amounts of MeOH and dried in vacuo over NaOH. Yield 0-41 g. Analysis indicated considerable loss of sulphur from the Pd(SCrCI~)2 and that the product had empirical formula of about PdCrH~rN4C13S0.36. 1. S. E. Livingston, Quart. Rev. 386 (1965). 2. W. Beck, K. H. Stetter, S. Tadros and K. E. Schwazhans, Chem. Ber. 100, 3944 (1967). 3. R. S. Nyholm, J. F. Skinner and M. H. B. Stiddard, J. chem. Soc. (A) 38 (1968); R. S. Nyholm and B. R. Hollebone, J. chem. Soc. (A) 332 (1971). 4. R. H. Fenn and G. R. Segrott, J. chem. Soc. (A) 3197 (1970). 5. R. H. Fenn and G. R. Segrott, J. chem. Soc. (A) 278 (1970). 6. C. R. Lucas and M. E. Peach, lnorg, nucl. Chem. Lett. 5, 73 (1969): Can. J. Chem. 48, 1869 (1970).
3268
Notes
Reaction with triphenylphosphine. An ethanol solution of Ph3P (5"25 g in 124 ml) containing 1.34 g of Pd(SCeCID2 was refluxed for 4 d. The brown mixture was poured into 250 ml of EtOH and filtered after boiling for 15 min. The brown insoluble product (1-08 g) was shown by its i.r. spectrum to be Pd(SCnCID2. Evaporation of the solvent from the filtrate left Ph3P (found M.P. 80°; lit. M.P. 80°). .Reaction with ethylene-bis(diphenyl phosphine). Pd(SC6CIs)2 (1.34g) was added to an ethanol solution of EDP (1 '59 g in 200 ml) and the mixture refluxed for 72 hr. The yellow product was filtered off, washed with EtOH and Et20 and air dried. Yield, 2"0 g. Anal. Calcd. for C3sH24CIloP2S2Pd: C, 42"78; H, 2.27; S, 6.01. Found: C, 42"84; H, 2.40; S, 5.98. The product is soluble in MeOH, EtOH, CHCI3, CH2C12, C1CH~CHzC1, C6Hr, Py, DMF, DMSO and Me.2CO. Complex ions A solution of PdCI2 (0.0925 g in 20 ml H20 + one drop HCI) was added to an aqueous solution of CrCIsSH (0.561 g in 20 ml H20 with sufficient N a O H to achieve solution). This solution was filtered and added to a solution of Ph4AsC1 (0.420 g in 10 ml HeO): the red brown precipitate was filtered off after an hour and washed with water. Yield 0.667 g. M.P. 242°d. Anal. Calcd. for C72H40As2C120PdS4: C, 43.27; H, 2.02; Pd, 5.32. Found: C, 42.99; H, 2.05; Pd, 5.46. The product was soluble in Me2CO, insoluble in EtOH, Et20, CrHr, and pet. ether. The compound (PI~As)2[Ni(SCrCI5)4] was prepared similarly starting from Ni(NO3)z.6H20 (0.145g). Yield 0.429g. Anal. Calcd. for Cr2H4oAs2C120NiS4: C, 44.33; H, 2.07; Ni, 3.01. Found: C, 44.56; H, 2'58; Ni, 3'31. The potassium salt K2[Pd(SCnCIs)4] was prepared by adding an alkaline solution of CeCIsSH (1.13 g in 5 ml) to K2PdCI4 (0"33 g in 20 ml H20). The dark red product separated immediately, which, after standing, was filtered off, washed with H20, EtOH, and Et20, then air dried. Yield 0.98 g. Anal. Calcd. for C24C120K2PdS4: C, 22.54; H, 0.00; S, 10.04. Found: C, 22.70; H, 0.64; S, 9"18. Attempts to isolate a pure Bu4N + salt from an analogous reaction by adding an alkaline solution of CeCIsSH to a solution of Bu4NBr and K2PdCI4 failed. The compound Kz[Pt(SCrCIs)4] was prepared analogously, starting from K2PtCI4 (0"214 g). Yield 0.642 g. Anal. Calcd. for C24CI2oK2PtS4: C, 20.61 ; H, 0.0; S, 9.17. Found: C, 21.05; H, 0.3; S, 9-03.
Acknowledgement-The financial assistance of the National Research Council of Canada for an operating grant and a studentship (C.R.L.) is gratefully acknowledged.
Department of Chemistry Acadia University Wolfville Nova Scotia Canada
C. R. LUCAS* M. E. P E A C H K. K. R A M A S W A M Y t
* Present address: Inorganic Chemistry Laboratory, Oxford University, England. tPresent address: Humphrey Chemical Company, New Haven, Conn. 06473, U.S.A.
J. inorg, nucl. Chem., 1972, Vol. 34, pp. 3268-327 I.
Pergamon Press.
Printed in Great Britain
The crystal structure of a S r U O 4.000 (Received 24 January 1972) DURING a study of the phase systems MO-UO2-O2 (M = Ba, Sr, Ca and Cd), a monophasic sample of c~ SrUO4.ooo was prepared and characterized by X-ray and chemical analyses. The sample, yellow in colour had a mole composition of SrO/UO~.oo~ _+o.ooz= 0.998 and X-ray examination using the HaggGuinier camera showed the absence of any of the strong reflections to be expected from the phases