摘要:

1032 J.C.S. DaltonCationic Ruthenium Systems. Part 3.l Preparation and Characteriz-ation of Cationic Dienehydridotris( phosphine)ruthenium Complexes :The Crystal and Molecular Structure of (q-Buta-I ,3-diene)tris(dimethyl-phenyl phosphine) hyd ridorut hen iu m( 11) Hexaf I uorophosphateBy Terence V. Ashworth and Eric Singleton," National Chemical Research Laboratory, Council for ScientificMichael Laing and Lynn Pope, Chemistry Department, University of Natal, Durban 4001, Republic of Southand Industrial Research, Pretoria 0001 , Republic of South AfricaAfricaThe stable salts [RuH(diene)L,] [PF,] (1 : diene = cyclo-octa-I ,tj-diene (cod), hexa-1,3-diene, or buta-1,3-diene,L = PMe,Ph; diene = cod, L = P(OMe),, P[(OCH,),CMe], PPh,(OMe), PMe,, or PMePh,) have been preparedfrom the salt [RuH(cod) (NH,NMe,),] [PF,], and have been characterized by i.r., microanalytical, and l H n.m.r.measurements.The crystal structure of [RuH(C,H6) (PMe,Ph),] [PF,]. ca. 0.5CH,C12 has been determined. Theyellow crystals are monoclinic, space group P2,/n, a = 17.85, b = 18.96, c = 10.31 8, p = 106.1 O. The structurehas been solved by the heavy-atom method and refined by least squares to R 0.070 for 2 429 observed datacollected on a diffractometer using graphite-monochromatized Mo-K, radiation. The ruthenium has a distorted-octahedral co-ordination geometry. It is bonded to all the carbon atoms of the butadiene molecule; Ru-C 2.1 4-2.38 8. The phosphine ligands have a fac configuration ; Ru-P 2.28-2.34 8, P-Ru-P 94-1 00".The butadienemoiety is approximately planar, with bond lengths of 1.48, 1.34, and 1.43 a (estimated standard deviation 0.03 8).The position of the hydride ligand is not directly observable but can be inferred from the arrangement of the otherligands in the cation.ALTHOUGH hydrido-olefin complexes are postulated asthe intermediates in hydrogenation ,2 isomerization ,, andoligomerization 4 reactions, very few have been character-ized and only one, [IrH(C4He,)(Ppri3),] (C,He, = buta-1,3-diene), has been elucidated ~tructurally.~ I'revioustreatments of hydridoruthenium(I1) phospliine com-plexes with dienes gave e, only unstable products wliichcould not be fully characterized. Believing this in-stability to be a consequence of steric repulsions betweenthe bulky PPli, ligands of the precursors, we undertookthe present study to see whether stable dienehydrido-complexes could be prepared by using smaller ligands.We have found that complexes of the type [RuH-(diene)L,] I- (L = a tertiary phosphorus donor ligand)can be prepared by a simple, generally applicable, route,provided that the size of the ligand L allows the complexto adopt a facial configuration.RESULTS AND DISCUSSIONTreatment of an argon-saturated solution of [ RuH-(cod)(NH,NMe,),][PF6] (1) in methanol at 20 "C with3.1 mol equivalents of the appropriate ligand I, effectedprecipitation within ca.5 min of tlte salts LIiuH(cod)L,]-[PF,] (2; L = PMe,, PMe,Ph, PMePh,, PYh,(OMe),P(OMe),, or P[(OCH,),CMel). Tlie cyclo-octa-1,5-diene(cod) ligand in (2; L = PR!Ie,Ph) was readily replacedand this lability was used to extend the range of diene-hydrido-complexes.Thus, (2 ; L = PMe,Ph) dissolvedin refluxing methanol to give a dark red solution whichturned yellow on treatment with buta-1,3-diene or hexa-1,3-diene and deposited the salts (2; L = PMe,Ph;1 Part 2, T. V. Ashworth, M. J . Nolte, 17. Singleton, and M.Laing, J.C.S. Dalton, 1977, 1816.2 K. E. Hanson, S. I<. Gupta, and D. J. Brown, Cliem. Rev.,1973, 73, 21.3 R. F. Heck, ' Organotransitioii Metal Chemistry,' AcademicPress, New York, London, 1974, 76.4 M. 11. Taqiii Khan and A. E. Martell, ' Homogeneous Cata-lysis by Metal Complexes,' Academic Press, Nccv York, London,1974, vol. 2, p. 99.diene = buta-1 J-diene or hexa-1,3-diene) on cooling.It appears that the red species is a solvated cation ofthe type [RUH(PM~,P~),(HOM~)~]+ (x is probably 2).Attempts to isolate a metal complex from the redsolution were unsuccessful.However, addition ofanother mol equivalent of PMe,Ph to the red solutionproduced a solution, of similar colour, which is believedto contain [RuH(PMe,Ph),(HOMe)] + since treatmentwith H,, CO, or PMe,Ph (1 mol equivalent) gave [RuH,-(PMe,Ph),] [PF,] ,' [RuH(CO) (PMe,Ph),][PF6],7 and[RuH(PMe,Ph),] LPFS] respectively. Although the redspecies ' [RuH(PMe,Ph),(HOMe),]+ ' reacted with H,and CO, the products were extremely soluble and havenot been isolated in the purity required for completecharacterization.Attempts to prepare the complex [RuH(cod)-(PPh(OMe),),] [PF,] by similar procedures were un-successful; instead only the known salt [RuH-(PPh(OMe),),]~ Pli6] was isolated.In contrast, thecorresponding cations [RuHL,] I- {L = P(OMe), orP[(OCH,),CMe]} could not be prepared from the appro-priate dienehydrido-complexes (2) ; only starting ma-terial was recovered under all the reaction conditions.In view of the similar donor properties of these threeligands, the only plausible reason for this difference isthat [RuHL,] + is thermodynamically more stable than[RuH(cod)L,] I-, but a sterically induced labilization ofthe cod ligancl does not occur with the relatively smallerligands P(OMe), and PI (OCH,),CMe]. A similar situ-ation was found with PMe, and PMe,Ph; substitution5 G.Del Piero, G. Perego, and M. Cesari, Gazzetta, 1975, 105,529.J. R. Sanders, J.C.S. Dalton, 1973, 743; P. S. Hallman, B. R.McGarvey, and G. Wilkinson, J . Clzeiiz. SOC. ( A ) , 1965, 3143.7 T. 17. Ashworth and E. Singleton, J.C.S. Chem. Comm.,1976, 706.8 J . J . Hough and E. Singleton, J.C.S. Chenz. Comvn., 1972,371.9 D. ,2. Couch and S. I). Robinson, Igzopg. Chim. A d a , 1974, 9,391978 1033of the cod ligand in [RuH(cod)(PMe,),][PF,] by PMe,took place only after several hours and even thenmixtures of the starting material and the new complex[RuH(PMe,),][PF,] were obtained. In contrast, awarm solution of [RuH(cod) (PhIe,Ph),] [PF,] with excessof PMe,Ph formed [RuH(PMe,Ph),][PF,].A doublet ( J 94 Hz) of triplets ( J 18 Hz) observed forthe hydride resonance in the 100-MHz lH n.m.r.spectrumof [2; L = P(OMe),] is consistent with a f a c arrange-ment of phosphite ligands. A 3lP nucleus co-ordinatedtrans to a hydride ligand normally gives rise to a P-Hcoupling constant in the 60-180 Hz region, while thecoupling constant when the 31P and hydride nuclei arein mutually cis positions is smaller, in the range 5-30Hz.l0 The hydride pattern recorded at 60 MHz wascomplex, indicating second-order effects. The signalsdue to the pliosphite methoxy-protons consisted of adoublet ( J 5 Hz) at T 5.68 (9 H), and a 1 : 2 : 1 triplet( J 2 Hz) at T 5.87 (18 H). Although this patternnormally indicates l1 a meridional configuration ofphosphorus-donor ligands, and thus conflicts with theevidence of the hydride pattern, it must be assumedthat cis ' virtual coupling ' occurs in this complex.The lH n.m.r.spectrum of (2; L = P[(OCH,),CMe]) wassimilar and hence a f a c arrangement of phosphite ligandswas also assigned to this complex. These together withother l2 examples illustrate the danger of using thepatterns arising from ' virtually coupled ' phosphinesystems to assign stereochemistry. In contrast, the l H1i.m.r. spectrum of (2; L = PMe,) conformed with thatexpected for the f a c isomer; a doublet ( J 8.0 Hz) atT 8.29 (9 H) and a ' filled-in ' doublet (.J* 8.0 Hz) atT 8.58 (18 H) for the methyl protons, and, a t high field38FIGUliE 1(7: 16.02), a doublet ( J 56) of triplets ( J 28) due to thehydride ligand which appears as a 1 : 2 : 2 : 2 : 1 quintetlo H.D. Kaesz and R. B. Saillant, Chew. Rev., 1972, 72, 231.J. M. Jenkins, M. S. Lupin, and B. L. Shaw, J . Chew SOC.( A ) , 1966, 1787.because of coincidental overlap. The labile nature ofthe other complexes (2) in solution produced broad un-resolved resonances without any characteristic 1H-31P or 0 IFIGURE 2 Projection of thc iiiolecule on t o thc plane of the threephosphorus atoms. :Irrows indicate the three methyl groupswliicli are foi-ced tvgcther aiicl for which the liu-l-'-C(niethyl)niiglc is 122"31P-311' coupling, thus making stereocliemical assign-ments from the lH n.m.r. impossible.The presence of a hydride ligand in (2; diene = buta-1,3-diene) could not be detected from either i.r.or l Hn.m.r. evidence. I t was then thought possible that an3-ally1 ligand might have been present, since these areknown l3 to form on reaction of conjugated dienes withmetal hydrides. It was thus decided to determine thestructure of this complex by a single-crystal X-raydiffraction study with the aims of discovering (i) theprecise formulation of the complex and (ii) the arrange-ment of the phosphine ligands to see whether the labilityin solution was a consequence of interligand contacts.The overall molecular geometry of the cation is givenin Figure 1. The ruthenium atom has a distorted-octahedral co-ordination geometry with the six sitesoccupied by the three Y atoms of the phosphine ligands,the two ' double bonds ' of the butadiene molecule, andthe liydride ligand.The phosphine ligands are in afnc configuration, and the four carbon atoms of thebutadiene are all bonded to the ruthenium atom: Ru-Clengths lie between 2.14 and 2.38 A.The mean plane of atoms P(1), P(2), and P(3) isapproximately parallel to that defined by C ( l ) , C(Z),C(3), and C(4) of the butadiene system. A projectionon to tlie latter plane (Figure 2) shows that the butadienegroup is nearly symmetrically placed with P(1) trans tothe C(2)-C(3) bond, while tlie projections of Ru-P(2)l2 G. Nl. Bancroft and E. T. Libbcy, Cnnad. .T. Chrm., 1873,51,1482.l3 lief. 3, p. 1201034 J.C.S. Daltonand Ru-P(3) are approximately perpendicular to bondsC( 1)-C(2) and C(3)-C(4) respectively. The hydrogenatom bonded to the ruthenium lies approximately transto P(3) and in the region between C ( l ) and P(1).Thisassignment is supported by the small but systematicdistortions in the arrangement of the other atoms whichare bonded directly to the ruthenium (see Figure 2).Ru-P(3) = 2.28 A, 0.05 A shorter than the mean of theother two Ru-P bond lengths. This difference may notbe real, because M-P bonds trans to hydride tend to belonger rather than shorter.14TJnfortunately, the positions of the C atoms of theimtadiene group are not as well defined as is desirable.T l i c ~ imprecision is caused by a combination of thedisordering in the [PF,]- anion and the disordered (andThe separations between pairs of C atoms for thesemethyl groups are considerably smaller than 4 A (thesum of their usual effective contact radii) : C(17)-C(27)3.71, C(27)-C(38) 3.74, and C(38)-C(17) 3.69 A.Thereasons for these distortions and their effect on the re-activity of the Ru(PMe,Ph), system have recently beendiscussed.lI t is evident that the isomer with the mey configurationof the phosphine ligands cannot exist because of theexcessive strain that would result from the contactsbetween the butadiene group and the phosphine groupwhich would occupy the site where the hydride ligandis in the f a c isomer. In fact a f a c configuration ofphosphites was obtained even with the smallest ligandP[ (OCH,),CMe] and hence we assign this stereochemistryTABLE 1Analytical and spectroscopic data for the complexes";PaComplex Colour (O,/ C)i i l l i W(cod)L3][PF6]1, = PMe,Ph Colourless 138PMePh, Yellow-brown 155PMe, ColourlessPPh, (OMe) Yellow-brown 169P (OMe) , Colourless 142Analyses (%) Infrared(cm-') lH N.m.r.(7) C H v(RuH) L -I49.657.6(59.1)34.7(35.0)56.0(56.2)28.0(28.0)(49.9)6.1(6.0) 1980m5.4 2 080w 8.0(br, PMe)(5.5)6.9(6.9)( 5 42 OOOw 8.30(pt, J* 8, PMe,), 11.8br (RuH)1 985w 6.28br, 6.7 (br, olefinic protons, 4 H)8.29 (d, J 8.0, PMe,, 9 H), 8.58 (pt, J* 8.0, PMe,,6.80 [pt, J* 11, P(OMe)]1 960s 5.68 d, [ J 5, P(OMe),, 9 HI, 5.86 [t, J 2, P(OMe),,18 H), 16.02 [d, ( J 56) oft's ( J 28)(RuH)]5.35.5(5.5) 18 HI, 15.9 [d, ( J 94) oft's (J 18)(RuH)]Colourless 213 34.7 5.0 1 950s 5.67 [d, J 5, P(OCH,),, 6 HI, 5.85 [t, J 2, P(OCH,),,12 H], 9.12 (s, CMe, 3 H), 9.25 (s, CMe, 6 H), 15.7 (34.6) (5.0)P[(OCH,),CMeI(m, RuH)[RuH(C,H,) (PMe,Ph),][PF,] Yellow 150 46.2 5.7 4.92 (br, olefinic protons), 8.30 (br, PMe,)(46.3) (5.6) G[KuH(C,H,) (PMe,Ph),][PF,] Yellow 154-156 48.5' '5.8.7.20 (br, CH, 4 H), 8.24 (pt, J* 5.5), 8.55 (d, J 5,(48.6) (5.7) PMe,), 12.5 (br, RuH)a Calculated values are given in parentheses. J values in Hz. Hydride resonance not observed. d C6H, = Cyclohexa-1,3-iliene.non-stoicheiometric) solvent molecule. The y co-ordin-ates of the C atoms of the butadiene molecule are closeto those of the C and C1 atoms of the solvent moleculeand thus are adversely affected by the disordering. Inspite of the imprecision, the trend of long-short-longC-C bonds does seem to be real.This effect has beenseen before l5 and, in addition, the systematic alternationof the C atoms above and below their mean plane (seeTable 3) was also observed. The reduction of theC-C-C angles to 118 and 119" is normal, and has beenobserved l5 in other butadienemetal complexes.The Ru-P-C angles in each of the phosphine ligandsshow the same distortion that was observed16 in the[Ru,C~,(PM~,P~),]~ cation : one Ru-P-CH, angle isclose to 122", while the other is far smaller, ca. 114".The three methyl groups indicated by arrows in Figure 2are those associated with Ru-P-C angles of ca. 122".l4 A. Immirzi and A. Succarelli, Cryst. Struct. Comm., 1972, 1,l5 G. Huttner, D. Neugehauer, and A. Razavi, Angew.Chem.317.Internat. Edn., 1975, 14, 352.to all the other dienehydrides prepared here. It isinteresting to note that for larger ligands the interligandrepulsions would prevent the formation of even the f a cisomer and this probably accounts for the inability tocharacterize dienehydridoruthenium(I1) complexes withsuch ligands as PPh,., We have recently found that thesalt [RuH(C,H,) (PMe,Ph),] [PF,] may also be obtainedby reaction of [RuH(PMe,Ph),][PF,] with buta-1,3-diene. A possible reason for the failure to isolate an3-ally1 derivative from this reaction is that the ligands inthe likely product, [Ru(q3-C,H,) (PMe,Ph),]+, would betoo crowded and, thus, the dienehydrido-structure withthree PMe,Ph ligands is sterically more favoured.Sterichindrance in the possible 1-3-3-ally1 complex has beeninvoked l7 previously to explain the preferential form-ation of [CoH(C,H,Me,) (PPh,),] (C,H,Me, = 2,3-di-methylbuta-1,3-diene), despite the existence of thecorresponding 1-3-?-ally1 complexes [Co ( C6Hll) (CO),]and [Co(C&ii) (PF,),].l8 M. Laing and L. Pope, Acta Cryst., 1976, B32, 1547.l7 P. V. Rinze, Angew. Chem. Internat. Edn., 1974, 13, 3361978 1035EXPERIMENTALThe salt [IiuH(cod) (NH,NMe,),] [PI;,] was prepared asdescribed previously.18 All the other reagents were ob-tained commercially and were not further purified. All theoperations were performed in an argon atmosphere withdry argon-saturated solvents. Melting points were deter-mined on a Kofler hot-stage apparatus and were corrected.Infrared spectra were recorded on a Perkin-Elmer model457 grating spectrophotometer and 'H n.m.r. spectrawith Varian A-60A and HA- 100 instruments.Elementalanalyses were carried out in the N.C.R.L. laboratory.Physical and spectroscopic data for all the new complexesare presented in Table 1.Preparations .-( q-Cyclo-octa- 1 , 5-diene)tris (dimethylplzenyl-phosphine) J8ydridoruthenium hexafluovop hosphate. Di-methylphenylphosphine (0.42 g, 3.1 mmol) was added to astirred solution of [IZuH(cod)(NH,NMe,),][PF,] (0.5 g,1 mmol) in methanol a t 20 "C. Within cn. 2 min a colour-less precipitate formed which was filtered off and re-crystallized from CH,CI,-EtOH a t 0 "C to give the requiredproduct as colourless prisms (0.6 g, yield 78%).Similarly prepared were: [RuH(cod) (PMe,),][PF,] as acolourless powder (0.33 g, 58%), [RuH(cod)(PMePh,),][PF,]as a pale brown powder (0.8 g, 840/,), [RuH(cod){PPh,-(OMe)},][PF,] as a yellow powder (0.8 g, 800/,), [RuH(cod)-(P(OMe),},] [I'F,] as colourless prisms (0.5 g, 67%), and[RuH(cod){ P[ (OCH,),CMe] },I [PI?,] as colourless prisms (0.5Reaction of [RuH(cod) (NH,NMe,),][PF,] with Excess ofP(OMe),.-Trimethyl pliosphite (0.75 g, 6.1 nimol) wasadded to a refluxing solution of [RuH(cod) (NH,NMe,),]-[PF,] (0.5 g, 1 mmol).After 1 h the solvent was evapor-ated off under reduced pressure and addition of methanolgave a colourless precipitate of [RuH(cod){ P(OMe),),][PF,].Under similar conditions P[(OCH,),CMe] gave [IiuH(cod)-(q-Buta- 1,3-diene) tris(dimethy1PhenyZpJ~osphine) hydrzdo-ruthenium HexafluorophosPhate.-On passing a stream ofbuta-1,3-diene through a suspension of [RuH(cod)-(PMe2Ph),]LPF,1 (0.38 g, 0.5 mmol) in warm methanol ayellow precipitate was obtained which was recrystallizedfrom CH,Cl,-MeOH mixtures to give the required productas yellow prisms (0.6 g , yield 81%).The correspondingcyclohexa- 1,3-diene complex was similarly prepared usingan excess of cyclohexa- 1,3-diene and was obtained asyellow prisms (0.6 g, yield 80%).Crystal-structure Detevmination of LRuH (C,H,) (I-'Me,Ph) ,I-[PI;',] .-Recrystallization of the complex from CH,CI,-MeOH gave well shaped, yellow, monoclinic crystals.C,,H,,FGP,Ru, M = 7 16, Monoclinic, spacegroup P2,/n, a = 17.85(2),0b = 18.96(2), c = 10.31(1) A,p = 106.1(1)", U = 3 305 A3, D, = 1.48 g c~ii-~, 2 = 4,D, = 1.44 g cm-,.Intensity data werecollected on a Philips four-circle difiractometer withgraphite-monochromated Mo-K, radiation ( A 0.710 7 A) for8 between 3 and 20".The w-28 scan technique was used;the scan width was lo, the scan time was 33 s, and thebackground was counted for 33 s. Of the 3 232 reflectionsmeasured, 2 429 were classed as observed, I > 1.650(1).Three reflections were used as standards and were re-measured after every 60 reflections; no crystal decom-g1 65%).{r[(ocH2)3cMe1 131 r P F G I *Crystal data.Structure solution and refinement.* For details see Notices to Authors No. 7, J.C.S. Dalton, 1977,Index issue.position was observed.Intensities were corrected forLorentz and polarization effects only; ~(Mo-K,) is 7.4 cm-l.The RuP, moiety was located from a Patterson map, andall the remaining atoms were found in the subsequentFourier maps. The structure was refined by the block-diagonal least-squares method with Ru, four P, and sixF atoms anisotropic and the C1 and all the C atoms iso-tropic. Weighting was proportional to 1/F for F > 50and to F for R < 50 with a proportionality constant thatgave a weighting of 1.0 for F = 50 (Fo ranged from ca. 10to 250). About half a molecule of CH,Cl, solvent wasfound to be disordered about the inversion centre a t O,O,&;thus, in the structure-factor calculations the C1 atom wasgiven the weighting 0.50 while that for C (of solvent) was0.25.Scattering factors for neutral atoms were used(' International Tables for X-Ray Crystallography,' 1962) ;that of the Ru atom was corrected for anomalous dispersion.The refinement converged a t R 0.070 for the 2 429observed data. Observed and calculated structure factorsand the thermal parameters are listed in SupplementaryTABLE 2Fractional atomic co-ordinates for [RuH(C,H,) (PMe,Ph),]-%la0.207 70(6)0.304 9(2)0.281 2(2)0.161 8(2)0.355 6(3)0.323 4(9)0.375 5(13)0.338 l(11)0.380 4(12)0.435 8(8)0.276 l(9)0.128 5(10)0.088 4( 10)0.114 O(10)0.376 6(7)0.454 6(8)0.504 7(9)0.478 3(9)0.402 l(10)0.348 l(8)0.367 8(8)0.268 2(8)0.322 9(7)0.287 9(8)0.389 5(9)0.421 4(8)0.388 l(8)0.369 3(9)0.106 6(8)0.025 7( 10)0.025 3(10)0.104 5( 10)0.146 7(8)0.089 7( 11)0.227 7(9)0.063 9(13)0.191 2(10)0.323 5(9)0.230 9(9)-0.015 O(11)- 0.007 ( 1 1)CWJYlb0.068 10(6)0.075 5 ( 2 )0.093 O(2)0.310 7(2)0.387 8(6)0.234 4(8)0.307 5(9)0.321 3(11)0.319 6(14)0.294 2(11)0.180 7(2)-0.052 l(9)-0.001 2(9)0.030 l(9)0.020 6(Y)0.002 2(7)0.015 9(7)-0.043 8(8)-0.109 6(9)-0.123 O(9)-0.065 7(8)0.153 O(8)0.061 9(8)0.012 5(7)-0.081 7(9)-0.109 2(8)-0.019 4(8)-0.079 8(8)-0.018 l(7)0.147 9(8)0.133 4(9)0.197 O(7)0.185 9(9)0.193 8(10)0.210 3(10)0.214 3(8)0.207 l(10)6.257 7(9)0.025 3(12)0.222 8(9)- 0.0 1 8 ( 10)zlc0.148 OO(10)0.036 3(3)0.366 3(3)0.107 5(4)0.716 7(5)0.710 2(14)0.717 4(17)0.857 5(16)0.595 6(16)0.804 2(18)0.643 9(27)0.203 3( 17)0.207 7j17)0.093 3(17)-0.025 O(17)0.080 6(12)0.149 G(14)0.188 2(16)0.157 l(16)0.086 8(18)0.044 7(14)0.040 5( 14)0.458 7(13)0.553 4(14)0.621 4( 16)0.501 3(15)0.434 8(14)0.401 5(15)0.480 O(16)- 0.146 9( 14)0.597 8(16)- 0.069 5 ( 14)-0.107 7(18)-0.251 2(19)-0.337 l(18)-0.298 8(18)-0.161 2(14)0.201 5( 19)0.145 3(17)0.561 5(24)0.547 ( 16)* Weighting for C1 was 0.5 and for C(s) was 0.25.Publication No.SUP 22267 (17 pp.).* The final difference-Fourier map showed that the [PFJ ion was disorderedla T. V. Ashworth, E. Singleton, and J. J. Hough, J.C.S.Dalton, 1977, 18091036 J.C.S. DaltonTABLE 3Bond lengths (A) and angles (").Estimated standarddeviations: Ru-P 0.01; P-C and Ru-C 0.02; C-C0.03 A; of bond angles 1"P(l)-C(ll) 1.86 Ru-P(l) 2.34P(l)-C(17) 1.84 Ru-P(2) 2.32P(l)-C(18) 1.84 Ru-P(3) 2.28P(2)-C(21) 1.85 Ku-C(l) 2.38P(2)-C(27) 1.84 Ru-C(2) 2.14P(2)-C(28) 1.83 Ru-C(3) 2.17P(3)-C(31) 1.84 Hu-C(4) 2.26P(3)-C(37) 1.88 C(1)-C(2) 1.48P(3)-C(38) 1.85 C(2)-C(3) 1.34C(3)-C(4) 1.43Mean (Ph)C-C(Ph) 1.39 5 0 . 0 7P(l)-Ru-P(2) 100 C( 1)-c (2)-C( 3) 119P( 2)-liu-P( 3) 94 C(2)-C(3)-C(4) 118P( l)-Ru-P( 3) 98Ru-P(l)-C(17) 124 C(17)-P(l)-C(lS) 100Ilu-P( 1)-C ( 18) 1 13 C(ll)-l'(l)-C(l8) 100Ku-P( 1)-C( 1 1) 1 13 C( 11)--P( 1)-C(17) 103Ku-P( 2)-C( 2;) 112 C ( 2 1)-P( 2)-C (27) 100Ku-P(2)-C(2r) 122 C (27)-P( 2)--C (28) 10 1Ku-P(3)-C(31) 114 C (3 1) -l'( 3)-C (3 7) 102Ru-P(3)-C(37) 115 C( 37)-I'( 3)-C (38) 10 1Ku-P( 3)-c (38) 122 C (3 1) -1' (3) -C (3 8) I 0 2Ru-P( 2)-C( 28) 1 17 q( ?l)-P( 2)-C( 28) 102about the F( l)-P(4)-F(2) axis and that the anisotropicthermal parameters derived for the I; atoms were inadequateto describe the disorder. Final positional parameters aregiven in Table 2, bond lengtlis and angles in Table 3. Thenumbering system within the cation is shown in Figure1.The dis-order of the [PFJ- anion is non-random. F(1) is welldefined while the thermal ellipsoids of P(4) and F(2)correspond to a pendulum-like motion. Superimposed onthis there is a large aniplitude of oscillation (or disorderingbetween two orientations) for the four F atoms in theTABLE 4Plane of butadiene moietyDirection cosines relative to :7 7x Y 20.605 0.755 0.253Description of the ~~en.afluorop~~osphate anion.Deviations (A) from the plane:C(1) -0.02, C(2) 0.04, C(3) -0.04, C(4) 0.02equatorial plane. Disordering of a [PITG]-- anion is notunusual, but in this case the distinctly snialler motion ofF(1) can be rationalized. It lies below lCu, in contact withphenyl rings 1 and 2, and with carbons C ( l ) and C(4) oftlie butadiene group; one is even tempted to ask thequestion ' Is there a Ru-H - - - F liyclrogcn bond? ' TheRU - - - I; separation is 4.96 A.We tliaiik Dr. G. Gainer, National Physical ResearchReceived, 23vd August, 197711,aboratory' C.S.I.R. for collecting the intensity data.[ 7/ 151

ISSN:1477-9226    

DOI:10.1039/DT9780001032

出版商:RSC    

年代:1978

数据来源: RSC