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684 J.C.S. DaltonDithiocarbamato- and Carbonyldithiocarbamato-complexes ofRhenium-(!), -(in), -(Iv), and -(v) tBy John F. Rowbottom and Geoffrey Wilkinson," St. Mary's College, Twickenham, and Inorganic ChemistryLaboratories, Imperial College, London SW7 2AYDithiocarbarnato-complexes of rhenium such as Re(CO)(S,CNR,), (R = Me, Et, PhCH,), ReCI,(S,CNR,),(R = Et, PhCH,), and Re,02S{S,CN(PhCH2)2)4, and complex ions such as [Re(S,CNEt,),]+ and [Re(CO),-(S,CNEt,)X]- (X = CI, I), have been prepared by interaction of Re(CO),CI and thiuram disulphides.Interaction of TI(S,CNEt,) and Re(CO),CI leads t o [Re(CO),(S,CNEt,)], which is easily cleaved by CO,pyridine, and PPh, t o Re(CO),(S,CNEt,) (L).The reaction of ReCI,(PPh,), w i t h [Et,NCS,], leads t o [Re,CI,(Et,NCS,)5]CI, as well as ReCI,(S,CNEt,), and[Re(S,CNEt,),]+.PREVIOUS studies lp2 on rhenium dithiocarbamato-cornplexes have been extended.Spectroscopic data for newcompounds are collected in the Table. The electro-chemistry of certain of the compounds will be describedseparately.subsequent X-ray diffraction study 3 of the diethyl-dithiocarbamate showed the compound to be the seven-co-ordinate monocarbonyl with a distorted pentagonalbipyramidal structure (I). The high oxygen analyseson different samples at different times were due to aInteraction of Tetra-alkylthiuram Disulphides with wrong blank determination and to wrong processing.[Re!dtc),] [ReCI,(dtc)] + ReCl,(dtc),Re(C0) (dtc),[Re (d tc)] / [ ReCl (CO) 3(dt~)]iii /J\iv[Re (CO) 3 (dtc) I 2 [Re(dtc),IISCHEME 1 dtc = diethyldithiocarbamate.Reagents: i, in benzene; ii, in acetone; iii, NaBPh, in acetone; iv, Bun4N, NaI,in acetoneRhenium Carbonyl Chlorides.-Scheme 1 summarises theprincipal reactions investigated. The main productsfrom the interaction of pentacarbonylchlororhenium(1)with [R2NCS& (R = Me, Et, and PhCH,) in acetone,tetrahydrofuran, toluene, etc., are brown crystallinecompounds of stoicheiometry Re(C0) (S2CNR2)3. ForR = Et, the same product is also obtained fromRe2C12(C0)8, Re,(CO),,, and ReCl(CO),(PPh,),. Thecompounds are monomeric and diagrnagnetic and haveonly one C-0 stretching frequency. Although weoriginally believed them to be dicarbonyls on the basisof the only really critical analyses, i.e.of oxygen, whichwere in excellent agreement with calculated values,t No reprints available.J. F. Rowbottom and G. Wilkinson, J.C.S. Dalton, 1972,J. F. Rowbottom and G. Wilkinson, Inorg. Nuclear Chem.826.Letters, 1973, 9, 675.The i.r. spectra of the complexes in regions character-istic for co-ordinated dithiocarbamate showed a single7 2Irs'iS. R. Fletcher and A. C. Skapski, J.C.S. Dalton, submitted* Dr. G. Reuter, Alfred Bernhardt Mikroanalytisches Labora-for publication.torium, personal communicationInfrared a and nuclear magnetic resonance b spectral and analytical data for rhenium dithiocarbamate complexesAFound (y.6)Re(CO)(S2CNPlle2),Re(C0) (S,CNE t&V(CN)1540s1505s1480s1520s1510s1499s1 ROSS1590s1495s1520s1495s1498s1518s1522s1530s1525s1520slS25s1535s1515sl b V 5 S1515s1490s,bcV(CS,)1005m975mlOl5m995m1025m990m,brlOOOm980m995m(980sh)995m993m999m999mi u i o w a99ow985w1025w dlOOOw965w1025w dlOOOw975wlO0OwlOOOwl O O O m(970sli)9951nlOOOm1020111 dlOOOm985m1020w 8995WlOOOm980mOther bands e 7 Values C H N Hal6.9 CH, 20.9 3.3 7.06.5 quartet CH2 29.2 4.6 6.42.5 f Ph 53.3 4.0 3.75.0 CH,23.5 2.4 3.2;!!:I (ReS) 8.9 triplet CH,33ow0 Re S M ' k H3.8 34 31.0 540 20.9 3.22.6 27 28.2 690 29.2 4 6930 53.6 4.110.6 830 23.0 2.4Re(C0) (S,CNP,CH,)3 1870s2030s2005s1955s1920s2090m c1995s1982s1945s1915w2010s1922s1905s3.0 460Re( CO),(S,CNE tz) (PPh,) 690 45.9 3.7 46.4 3.8 1.8 {5.OP]1894s1910s1890s(1850sh)[Re(S,CNEt2),l[Rc(CO),C1(S,CNEt,)] 1995m1895sRe(C0)3(S2CNEtl)(C6H,N) 1998m 470 31.4 3.0 31.2 3.1 2.827.5 4.2 5.6 4.1 25.7 27 3 4.11885s1860s,br1895s[Re(S,CNEt,),][Re(CO),CI(S,CN~tz)],C6H6 1995111 675s (C,H,) 2.7 singIet CH 31.4 4.2 5.2 2.66.6 quartet CH,)(ReS)3.5 29 31.2 4.31885s ,","8; }(ReCI) 8.9 triplet CH,36.0 5.5 3-6 16.51860s,br[Bun,N][Re(CO),I(S,CNE t,)] 1999m1960m1895s1865s[Bun4Nl [Re(CO),(Cl)(S,CNEt,)l 1996m 01890s.br6-4 9.1 36.6 5.8[Re( SaCNE ta),]BPh,1860s;br48.5 5.5 4.9 48.1 5.520.7 3.626.5 4.429.5 4.940 27.5 23.9 4.021.0 3.5 5.1 34.3[Re(S,CNEt,),l I[Re(S,CNEt,),]CI[Ke(S,CNEt,),] [ReCI,(S,CNEt,)]26.9 4.4 6.3 14.46.1 quartet CHI 30.2 4.8 6.7 4.19.2 triplet CH,24.1 3.8 5.7 10.83OOW370w } (ReS)350w315s 124.6 4.2 5.8 11.821.6 3.6 5.1 13.044.8 3.8 3.223.9 4.0 362m (ReS)(295sh)287s } (ReCI)(270sh)338m 355m ;;pm }(ReCl)ReCI,( S,CNE t ,)* 23.4 580 21.7 3.6ReCI,{S,CN(PhCH,)}, 960 45.0 3.84.2 17.9 1700 47.2 3.7 895s (Re=O) 2.5 (C-H) f 47.3 3.7 3.8 24;; ) (ReSol 5.0 (CIIe)} 315m I (ReSI3 290w 1 '970s IRe=Ol958m (Re=OjF50s (Re-0-Re).iOOm.sh > (ReSI48.0 3.6 3.5 47.7 3.7o Nujol and hexachlorobutadiene mclls.b Significant peaks only shown in cm-I. c Dichloroincthane solution; Me,Si reference. d Hexane solution. e All bands in this region included.basis of comparison between relevant spectra. l Acetone solution686 J.C.S.Daltonstrong C-N stretch typical of bidentate dithiocarbamate ;in the C-S region two medium bands were observed bothin mulls and in solution. The second band evidentlyarises because of the non-equivalence of the sulphuratoms in the dithiocarbamate group that has one S~ Y ~ Z I Z S to CO, as the two Re-S distances are significantlydiff went . The compounds are remarkably inert andcan be recovered unchanged after even prolonged treat-ment with refluxing pyridine, molten triphenylphosphine,sodium ethoxide in ethanol, hydrogen chloride inethanol, U.V. irradiation in benzene, and prolongedheating at 200 "C. The molybdenumAlo(K0) (S,CNMe,),, is isoelectronic with these rheniumcompounds and evidently has a pentagonal bipyramidalstructure as is known for Mo(NO)(S,CNBU,),.~~ At 25"multiple CH, resonances were observed which collapseto a singlet at elevated temperatures.By contrast therhenium complexes (R = Me, Et, PhCH,) are non-rigid and show only single CH, and normal ethyl andbenzyl resonances at 30" and the methyl and ethylcompounds show no change from -70 to +goo. Inthis temperature range, the alkyl groups are evidentlyequivalent. The reason for this difference from themolybdenum compound is not clear but it is of interestthat in several seven-co-ordinate dithiocarbaniates,TiX(S,CNR,),, the methyl and ethyl groups also remainequivalent .6 Since a mechanism involving dissociationwould imply greater chemical reactivity than is foundfor the rhenium compounds, a non-bond breaking pathis presumably involved.A second product from the interaction of ReCl(CO),and [Et,NCS,], in acetone is a golden-brown crystallinesolid of stoicheiometry Re,Cl(CO),(Et,NCS,)5. On re-crystallisation from acetone-benzene, a benzene solvatewas obtained. The presence of benzene was shown byanalysis and i.r.and n.m.r. spectroscopy, the latter beingconsistent with one benzene per five dithiocarbamategroups. The chloride is a 1 : 1 electrolyte in nitro-methane ' ( A M = 86.5 Q-l cm2 mol-l; c lo-") but sinceno rational structure with a univalent dirhenium cationcan be accommodated, rhenium must be present in bothcation and anion. These ions could be separated andidcn t ified.From acetone solutions of the chloride, sodium tetra-plienylborate gives black crystals of the diamagneticconiplex [Re(S,CNEt,),][BPh,].This too is a 1 1electrolyte in nitroinethane (A, = 84-2 i1-I cni2 niol-l;c l W 3 ~ ) . The i.r. spectrum shows only one C-X andone C-S stretch assignable to bidentate dithiocarbamateand since the compound is diamagnetic, the cation isevidently thc eight-co-ordinate rhenium(v) ion[Re(S,CNEt,),] . As far as we are aware the only otherexamples of eight-co-ordinate Re" are [Re(diars),Cl,]"and [Re(CN),I3-.During the reaction with sodium tetraphenylborate,5 (a) B. F. G. Johnson, I<. H. Al-Obaidi, and J. A. JlcCleverty,J . Chem. SOC. (A), 1969, 1668; R. Davis, M. N. S. Hill, C. E.Holloway, B. F. G. Johnson, and I<. H. Al-Obaidi, J . Chem.Soc.( A ) , 1971, 904; (b) T. I; Rrennan and I. Bernal, Chem. Conznz ,1970, 138.sodium chloride and a dimeric rhenium carbonyl (whichhad been obtained in other ways as discussed later)(separated. This reaction hence appears to be:[Re(S,CNEt,),][ReC1(CO),S2CNEt,] + NaBPh, -w[Re (S,CN E t ,) ,] BPh, + 8 [Re S,CNE t , (CO) ,] , -1- NaClAlthough we have not been able to isolate the chloro-anion, the corresponding iodo-species can be obtained.When the parent complex is treated with n-butyl-ammonium iodide and sodium iodide in acetone, palecream crystals of the salt [Bun4N1[ReI(CO),(S,CNEt,)]are obtained. This is diamagnetic as expected for ReTand is a 1 : 1 electrolyte in nitromethane (A, = 104-8R-l cm2 mob1; c 6 s lOP3~). The cation also can beobtained from the solution as black crystals of the iodide[Re(S,CNEt,),]I (A = 115 W cm2 niol-l; c 2 x 1 0 - 3 ~in MeNO,).Interaction of this iodide with anacetone solution of Bun4NC1 leads to [Re(S,CNEt,),]Cl.The position and number of C-0 stretching frequenciesin the anion and of the C-N and C-S bands in bothanion and cation in the separate complexes correspondto those in the parent compound which is hence[Re(S,CNEt,),] [ReCl(CO),S,CNEt,]. The v(CN) bandin [Re(S,CNEt,),]+ occurs a t higher frequency (1620cm-l) than that in the anion (1495 cm-l), which isconsistent with the differing oxidation states of themetal.The cation can also be obtained as [Re(S2CNEt,),]13from the products of the reaction of ReI(CO),(PPh,),with [Et,NCS,], and can be isolated as the tetraphenyl-borate from the products of interaction of ReCl,(PPh,),and [Et,NCS,j,.The interaction of ReCl(CO), and [Et,NCS,j, inbenzene, while giving mainly Re(C0) (S,CNEt,),, gives aby-product different from that formed in acetone, asjust described.A brown tarry solid separates and onrecrystallisation from acetone brown needles of stoicheio-metry Re,Cl,(S,CNEt,)5 are obtained. This substanceis a 1 : 1 electrolyte in nitromethane ( A M = 89 Q-l cm2mol-l; c 0-5 x 10-381) but unlike the previous salt it isparamagnetic (xs = 4.0 x c.g.s.u. at 297 K). Thei.r. spectrum indicates bidentate dithiocarbamate-Separation of the cation as before gives [Re(S,CNEt,),j-[BPh,! identical with that obtained previously.Al-though attempts to separate the anion have failed, theinitial product is clearly ReV( S,CNEt,),] [RelVCl,-(S,CNEt,)]. Other data are consistent with this formu-lation. The complex has Re-C1 stretches (Table) andthe magnetic moment calculated on this formulation,peff = 3.7 B.M. (297 K) is consistent with rhenium(Iv),d3 spin-free for the anion.A third product, Re(S,CNEt,),Cl,, can also be isolatedfrom the reaction in benzene. It forms red crystals, ismonomeric in benzene, non-conducting in nitromethane,and is paramagnetic with peE = 2.9 B.M. at 297 K.E:. C. Alyea, €3 S. Karnaswamy, A. N. Bhat, and K. C . Fay,Inorg. Nuclear Ghern. Lettcrs. 1973, 9, 399.Chtniistry,' John Tf7ile)- and Sons, London, 1972, 3rd ctln.7 W, J. Geary, Co-ovdinntio?l Chem.Ren., 1971, 7, 81.8 F. A. Cotton and G. IYilkinson, ' A4tivanced lnorgani1974 687The i.r. spectrum indicates bidentate dithiocarbamate,and has two Re-Cl stretching frequencies. The complexis evidently the octahedral cis-dichlorobis(diethy1-dit liiocarbamato) rhenium ( IV) , cis-ReCl,( S,CNEt ,) ,.This complex can also be obtained from the productsof the interaction in benzene of ReCl,(PPh,), and thetliiuram disulphide. The dibenzyl dithiocarbamato-analogue ReCl,[S,CN(CH,Ph)J, is obtained by inter-action of ReCl(CO), with tetrabenzylthiuram disulphideas red crystals with physical properties similar to thoseof the ethyl complex.The benzyltliiuram reaction however also gives otherproducts as shown by chromatography on alumina.One is the dark brown seven-co-ordinate Re(C0)-(S,CN(PhCH,),},.A third complex that forms browndiamagnetic needles has stoicheiometry Re,O,S-[S,CN(CH,Ph),], and is a dimer in CHC1,. In additionto the expected dithiocarbamate bands there is a stronghand in the i.r. region at 895 cm-l assignable asv(Re=O). Since there is no strong broad band at ca. 670c m l in thc region characteristic of the bridge in theRe(CO),], lo as well as (Et2PS,)Re(CO),,g RCS,Ke(CO),,lland (Et,PS,)Re(CO),L l2 (L = PPh3, AsPh,, SbPh,,py) and for the dimeric compounds a sulphur-bridgedstructure was proposed.The dithiocarbamate dimer probably has the Structure(11) where one of the S atoms of the CS, moiety links themetal atoms as in zinc l3 and cadmium l4 diethylditliio-carbamates.Rhenium(1) is thus octahedral as usual andthe splitting of the v(CS) band in the i.r. spectrutn(Table) can be accounted for. However, the i.r.criterion is by no means well established.(a) A split v(CS) has been interpreted 15n as indicatingunidentate S,CNR, in a well defined case. ( b ) A splitv(CS) is found as above in Re(CO)(S,CNR2), where onesulphur is ‘ trans ’ to CO and hence inequivalent.(c) The zinc and cadmium diethyldithiocarbalnates[M(S,CNEt,),], whose structures have been determinedby X-ray methods do not show a split v(CS) but onlysingle bands at ca. 990 cm-l. In Tl(S,CNEt,), in aNujol mull there is a splitting,15b but in solution there isonly one band at cn. 980 cm-l. In these cases, of course,[Re(CO),Cl(dtc)]-+ co+ir w i (co)[Ile,C1,(CO),] 2or 1 :Re(C0),(dtc)J2 __ Re(CO),(dtc)i i i \i- co1ReCl (CO) ,(PPh,) , __t Ke(CO) ,(PPh,) (dtc,) Re(C0) ,(dtc) (C5H5S)SCHEME 3 i, Tl(dtc); ii, PPh,; iii, pyridine; iv, SaBPh,; v, LiCl and Bun,XCllinear (@Re) ,O group in [O=Re (S,CNR,)] 0, thisthird complex is probably the sulphur-bridged dirnerrO=Re(S,CNR,)JS.Two bands at 448 and 435 cm-l inthe i.r. spectrum of the sulphur bridged dimer may betluc to the Re-S-Re group as these bands do not appearin the spectrum of the oxygen-bridged species.Interaction of Thallium Dithiocarbamates with RheniumCnvboizyl ChZorides.-The dimeric compound, [Re(CO),-(S,CNEt,)],, referred to earlier, and the related com-plexes Re(CO),(S,CNEt,)(L) (L = CO, py, PPh,) areformed in the reactions in Scheme 2.The dimer isquite readily cleaved by triphenylphosphine, pyridine,carbon monoxide, and chloride ion so that it seemsunlikely to contain a Re-Re bond and indeed this is alsosuggested by the ready formation from [Re(CO),Cl-(S,CNEt,)] - discussed earlier. This anion was alsodetected spectroscopically in the hexane extract iromthe products of interaction of the dimer with LiCl and[Bun,N]Cl in acetone.Rather similar dimers with other dithio-acids havebeen describcd, uis, (Et,PS,)Re(C0)3]2 and [(PhCS,)-29, 283.I: 1,indncr and I<. Matejcck, J . Organoinetallic Chem., 1971,lo 1%‘. Elieber a n d W. IiohIn, Chenz. B e y . , 1962, 102, 2787.I:. Imtlncr and H. Grimmer, J . Ovganometnllic Chem., 1970,l2 E 1,incincr md H.Bcrlte, J . OvganonzetaZZzc Chew., 1972, 39,lJ 31. Bonmiico, C;. Mazzonc, -1. \‘aciago, and L. Zambonelli,25, 4‘33.145.Acta C r y s t , 1965, 19, 898.no other ligands are present that might cause splittingdue to inequivalent sulphur atoms.C I S * c’NR2/It may be noted in respect of ~Re(CO),(S,CIC’Et,)],that the v(CN) band at 1520 cn-l is higher than inunidentate dithiocarbamates (1460-1470 cm I) .16 Thecompound also has four C-0 stretching frequencies as in[ReX(CO),(S,CNEt,)j- (X = C1, I) and Re(CO)3(PPli3)-(S,CNEt,) arid also in [(PhCS,)Re(CO),], in hexane.l4 .2. Uomenicano, L. Torelli, >I. Yacjago, and L. Zanibonelli,J . Chewz. Soc. ( A ) , 1968, 1351.l5 (a) 17. Bonati and K. LTgo, J . t)vgavio~~zctaZZic ihent., 1967,10, 257 ; ( b ) F.Bonati, S. Cenini, and K. r g o , ibid., 1967, 9, 395.A. Ihmenicano, -1. Vaciago, L. Zainl~oiiell~, 1’. I,. Loader,and 1,. _\I. I-enanzi, Chenz. Cowm., 1966, 476688 J.C.S. DaltonThe compound Re(CO),(S,CNEt,) loses carbon mon-oxide when heated in benzene and the dimer [Re(CO),-(S,CNEt,)] separates from solution.Interactioa of Tetraethylthiuram Disulphide with Bis-(tripheny1Phosphine)tetrachlo~o~henium ( IV) .- Interactionof ReCl,(PPh,), with (Et2NCS,)2 in refluxing benzenegives a red solution and an insoluble brown powder.The solution contains ReCl,(S,CNEt,), identical with theproduct from ReCl(CO), and thiuram disulphide dis-cussed above. The power on crystallisation frommethylene dichloride gives brown needles of stoicheio-metry Re,C14(S,CNEt2),.These are insoluble in acetonebut dissolve in nitromethane where the conductivity(AM = 153 L2-l cm2 mol-l; c 10-3~) is that of a 1 : 2electrolyte. Electrophoresis on paper using solutions ofr 1n-butylammonium perchlorate in dichloromethane assupporting electrolyte shows the presence of a browncation and a colourless anion which can be shown to bechloride. The complex can be formulated as (111) withoctahedral ReIV and eight-co-ordinate ReV.The magnetic susceptibility corresponds to a momentfor the ReIV atom of peg = 3-3 B.M. at 297 K. The i.r.band at 287 cm-l which has two shoulders can beassigned to the metal bridging chlorine system.When ReCI,(PPh,), and thiuram disulphide are re-fluxed in acetone, brown solutions are obtained fromwhich [Re(S,CNEt,),]+ is obtained.EXPERIMENTALAnalyses were by the Microanalytical Laboratory,Imperial College, and by A.Bernhardt, W. Germany.Infrared spectra were recorded on Perkin-Elmer 457 andUnicam SP 200 instruments. Molecular weights weremeasured on a Perlrin-Elmer-Hitachi model 115 osmometer.N.m.r. spectra were obtained on Perkin-Elmer R14 (100MHz) and R12A (60 MHz) spectrometers.All reactions were carried out under oxygen-free nitrogen.The following were prepared by published methodsReCl(C0) 5 , l7 Re,(CO) 8Cl,,18 ReCl,( PPh,) ,, l9 and [Et,hTCS,] ,.,OReOCl[S,CN(CH,Ph),], and Re,0,[S,CN(CH,Ph),]4 wereprepared by the methods used for the analogous ethylcomplexes published previous1y.lInteraction of Pentacnrbonylchlororhenium (I) and Tetra-ethylthiuram Disulphide in Acetone.-An acetone (80 cm3)solution of [Et,NCS,], (5 g), and ReCI(CO), (2 g) wasrefluxed for 6 h.The dark brown solution was evaporatedunder reduced pressure and the residual brown massextracted with ether (3 x 30 cm3) to leave a brown solid.This brown solid was extracted with refluxing benzeneW. Hieber and H. Schulten, 2. anorg. Claem., 1939, 243, 164.Method 111.(30 cm3) to leave a golden-brown solid (1.23 g, 36%) whichwas recrystallised from acetone-ether to give brown platesof the salt [Re(S,CNEt,)4][Re(CO)3(S2CNEt,)C1]. Re-crystallisation of this substance from acetone-benzenesolution gave brown plates of the benzene solvate[Re(S,CNEt,) ,] [Re(CO) 3(S,CNEt,) Cl] ,C,H,.Concentrationof the above benzene extract followed by addition of ethergave brown crystals of Re(CO)(S,CNEt,), (1.1 g, 27%).Interaction of Pentacarbonylchlororhenium(1) and Tetra-ethylthiuram Disulphide in Benzene.-A benzene (50 cm3)solution of ReCI(CO), (1 g) and [Et,NCSJ, (2-8 g) wasrefluxed for 7 h, cooled, and set aside at ca. 10" for 12 h.The brown deposit was collected and recrystallised fromacetone-benzene to give brown needles of the saltRe,(S,CNEt,),Cl, (0-15 g, 8%). The red-brown filtratewas concentrated to 25 cm3 and set aside for 3 days togive red crystals of the complex Re(S,CNEt,)Cl, (0.14 g,9.3%) ; these were recrystallised from acetone. The secondfiltrate was then treated with ether to give brown crystalsof the complex Re(CO)(S,CNEt,), (1-2 g, 63%).This wasdissolved in acetone, transferred to an alumina column, andeluted with ether-acetone (1 : 1).Carbonyltris(dimethyldithiocarbamato)rhenium(I11).- Anacetone (60 cm3) solution of [Me,NCS,], (1.44 g) andReCl(CO), (0.724 g) was refluxed for 4 h, cooled, andfiltered. The residue was recrystallised from acetone togive the product as brown crystals (0-8 g, 66%).Interaction of Pentacarbonylchlororhenium( I) and Tetra-benzylthiuram Disulphide in Benzene.-A benzene (30 cm3)solution of [(PhCH,),NCS,], (2.25 g) and ReCl(CO), (0.5 g)was refluxed for 1 h, cooled, and filtered. Ether (60 cm3)was added to the filtrate which, after rejection of theresidue, was concentrated to 20 cm3 when a further 30 cm3of ether was added.The red solid which separated during2 days was recrystallised from acetone to give red crystals(0.05 g, 5%) of the complex Re[S,CN(CH,Ph),],Cl,. Furtherconcentration of the filtrate and addition of ether gave abrown powder which was recrystallised twice from acetoneto give brown crystals of the complex Re(C0) [S,CN-The mixture was refluxed for 5 h and then evaporated;the residue was then dissolved in acetone (10 cm3). Theacetone solution was transferred to an alumina column andeluted with acetone-ether (1 : 1) ; the red-brown solutionwas concentrated and treated with ether to give a brownpowder. Recrystallisation from acetone gave the complexRe,O,S[S,CN(CH,Ph),], as brown needles (0-22 g, 20%).Tetrakis(diethyldithiocarbamato)rhenium(v) Tetraphenyl-borate.-An acetone (30 cm3) solution of [Re(S,CMEt,),]-[Re(CO),(S,CNEt,)Cl] (0.27 g) and NaBPh, (0.07 g) wasrefluxed for 2 h, cooled, and the white solid collected.Addition of ether to the filtrate gave dark brown needle-likecrystals of the complex (0.12 g, 50%).The white residuewas extracted with refluxing benzene. Concentration andcooling of the benzene extract gave cream crystals ofTetrabutylammonium Tricarbonyliodo(diethy1dithiocarba-mato)rhenate(I).-An acetone (10 cm3) solution of [Re-(S,CNEt,),][Re(CO),(S,CNEt,)Cl] (0-7 g), But,NI (0.2 g),and NaI (0-81 g) was refluxed for 2 h and cooled. Ether(15 cm3) was added to the mixture which was then set aside(CHJ'h)213 (0.42 g, 29%).[Re(CO) dEt2dtC)1 2'l8 E.VV. Abel, G. B. Hargreaves, and G. Wilkinson, J . Chem.l9 G. Rouschias and G. Wilkinson, J . Chem. SOC. ( A ) , 1966,465.2o R. Rothstein and K. Binovic, Rec. trav. Chim., 1954, 56, 76.SOG., 1958, 31491974 689overnight. Dark brown crystals were collected and re-crystallised from acetone to give the iodide Re(S,CNEt,),IThe filtrate was evaporated to dryness and the remainingsolid was extracted with dichloromethane. Addition ofether to the extract and cooling for 24 h gave white crystalsof the salt [ULP,N][R~(CO),(S,CNE~,)I] (0.1 g, 22%).Tetrakis (dithiocarbamato) rhenium (v) Tri-iodide .-A ben-zene (30 cm3) solution of ReI(CO),(PPh,), (0.6 g) and[Et,NCS,], (0.6 g) was refluxed for 12 h, cooled, filtered,treated with ether (60 cm3), and set aside overnight to givedark brown crystals of the compound (0.1 g, 137;).Con-centration of the remaining solution gave the complexRe(C0) (S,CNEt,), (0.1 g, 20%).Bis-p- (diethyldithiocarbamato) -bis[tricarbonylrlzeniu~ (I)]. -Method (A). A benzene (40 cm3) solution of [Re(CO),Cl],(0.86 g) and Tl(S,CNEt,) (0.91 g ) was refluxed for 8 h andthen filtered whilst hot; the residue was extracted with hotbenzene (30 cm3). The benzene solution was concen-trated (20 cm3) and cooled to give the complex, [Re(CO),-(S,CNEt,)],, as cream crystals (0-73 g, 80%).A benzene (30 cm3) solution of ReCl(CO),(0.36 g) and Tl(S,CNEt,) (0.35 g) was refluxed for 14 h,and then filtered whilst hot; the filtrate was set aside togive the complex (0.22 g, 52%).Tetracnrbonyl( diethyldithiocarbamato) rhenium ( I) .- Carbonmonoxide was bubbled through a suspension of [Re(CO),-(S2CNEt,)], (0.21 g) in benzene (30 cm3) a t 40" for 6 h togive a clear solution.The benzene was evaporated underreduced pressure a t 40'. The solid residue was extractedwith light petroleum (b.p. 60-80"; 3 x 20 cm3) and theextract was concentrated (10 cm3) to give the complex aswhite crystals (0.12 g, 550,/0).Tricurbonyl(cliethyldithiocarbamato) (fiyridine)rhenium( I ) .-A benzene (20 cm3) solution of pyridine (1 cm3) and[Re(CO),(S,CNEt,)], (0.4 g) was refluxed for 2 h, cooled, andfiltered. The filtrate was concentrated (10 cm3) and lightpetroleum (b.p. 60-80°; 20 om3) was added to give awhite solid.This solid was recrystallised from benzene-(0.2 g, 40%).Method (B).light petroleum to give the complex as white crystals (0-25 g,TricarbonyZ( triPheny@hos$hine) (diethyldithiocarbamato) -rkenium(1) .-Method (A). A benzene (20 cm3) solution ofReCl(CO,)(PPh,) (0.28 g) and Tl(S,CNEt,) (0-21 g) wasrefluxed for 1 h and then filtered whilst hot; the filtrate wasconcentrated (5 cm3). Addition of light petroleum (b.p,60-80°; 15 cm3) gave white crystals of the complex (0.12 g.A benzene solution (10 cm3) of [Re(CO),-(Et,dtc)], (0.43 g) and PPh, (0-3 g) was refluxed for 14 h,cooled, and ether added to give the complex (0.53 g, 76%).Interaction of Bis(triphenyZphosphine)tetrachlororhenizam-(IV) with Tetraethylthiuram Disulfihide. (A) A benzene(50 cm3) solution of (Et,NCS2), (1.4 g) and ReC1(PPh3),(1 g) was refluxed for 18 h, cooled, and filtered. The brownresidue of the salt Re,Cl,(Et,NCS,), (0.33 g, 38%) wascollected. The red filtrate was concentrated to 20 cm3 andether (50 om3) was added to give the complex ReC1,-(S2CNEt,), as red crystals (0.24 g, 37%).(B) An acetone (30 cm3) solution of [Et,NCS,], (1.26 g )and ReC1,(PPh3), (0.9 g) was refluxed for 18 h. Thesolvent was removed under reduced pressure and replacedby benzene (30 cm3). The solution was refluxed for ca.24 h, cooled, and filtered. The brown residue was collectedand recrystallised from dichloromethane-ether (1 : 1) togive the salt [Re,Cl,(S,CNEt,),] as brown needles (0.23 g,30%). The filtrate was treated with NaBPh, (0.36 g) andrefluxing continued for 3 h when the mixture was evapor-ated and the remaining solid dissolved in acetone. Theacetone extract was concentrated and treated with ether togive the salt, [Re(S,CNEt,)JBPh,, as dark brown crystals53%).55%).Method (B).(0.3 g, 26%).Acknowledgement is made to the donors of The PetroleumResearch Fund administered by the American ChemicalSociety for partial support of this research.[3/1951 Received, 24th September, 1973
ISSN:1477-9226
DOI:10.1039/DT9740000684
出版商:RSC
年代:1974
数据来源: RSC