摘要:

J. CHEM. SOC. DALTON TRANS. 1986 1129Reactions of [ Fe(cp)(CO),CI] (cp = q-cyclopentadienyl) with 3-Methylbut-2-enoic Acid and its Methyl Ester. X-Ray Crystal and Molecular Structure$ ofBis[ dicarbonyl (q-cyclopentadienyl) (3-methyl but-2-enoato) iron ( II)] hydrogenHexaf luoroantimonate and p-Chloro-bis[dicarbonyl(q-cyclopentadienyl)iron( II)]Hexaf luoroantimonateDomenico C. Cupertino, Marjorie M. Harding, and David J. Cole-Hamilton **tSchool of Chemistry, University of Liverpool, P.O. Box 147, Liverpool L69 3BXHelen M. Dawes and Michael B. HursthouseDepartment of Chemistry, Queen Mary College, Mile End Road, London El 4NSReaction of [Fe(cp)(CO),CI] (cp = q-CsHJ with AgSbF, in the presence of Me,C--CHCOOHaffords red [Fe(cp)(CO),(Me,C--CHCOOH)] [SbF,] with binding through the OH oxygen atom ororange [{Fe(cp) (CO),( Me,C==CHCOO)},H] [SbF,].The ester Me,C=CHCOOMe gives[Fe(cp) (CO),( Me,C=CHCOOMe) J [SbF,] for which i.r. studies imply binding through the carbonyloxygen atom of the ester group. The spectroscopic properties of these compounds are discussed.The X-ray structure of [(Fe(cp) (CO),( Me,C=CHCOO)},H] [SbF,] has been determined. Crystaldata: monoclinic, a = 29.901 (Z), b = 7.495(2), c = 14.006(2) A, = 100.65(1)*, space groupCZ/c, and Z = 4. The cation contains a centre of symmetry and is regarded as being made up oftwo Fe(cp) (CO), units each bound to a carbonyl oxygen atom of a symmetrical (Me,C=CHCOO),Hunit, with the two non-co-ordinated oxygen atoms hydrogen bonded together. The short0(9) O(9') distance [2.406(9) A] is indicative of a symmetrical hydrogen bond.The coplanarityof the two acid groups suggests some double bond delocalisation. In CH,CI, the compound[Fe(cp)(CO),(Me,C--CHCOOH)] [SbF,] slowly gives [{Fe(~p)(C0)~},Cl] [SbF,] for which the X-raycrystal structure shows an angle of 1 19.4(2)" at the bridging chlorine atom. The crystals of thecomplex are monoclinic, space group P2,/c, with a = 13.805(4), & = 12.301 (3), c = 12.457(3) A,and fl = 11 1.88(2)". The structure was solved via the heavy-atom method and refined to an Rvalue of 0.053 for 4 540 observed diffractometer data.Although many alkenes readily co-ordinate to transitionelements and can thus be activated towards the attack ofnucleophiles or the addition of small molecules, the stabilityconstants for alkenes bearing more than two substituents aregenerally very low.One of the metal fragments that will tolerategeminally disubstituted alkenes is [Fe(cp)(CO),] + (cp = q-cyclopentadienyl) for which the 2-methylpropene complex iswell known,' but readily exchanges 2-methylpropene withother alkene~.~.~ 1,2-Disubstituted alkene complexes of [Fe(cp)-(CO)J+ are also well known, e.g. with acenaphthene,'2,3 dihydrof~ran,~ tetramethylallene,6 and c648 cyclic al-kenes.'*3.' Alkenes that bear three or more substituents do notappear to co-ordinate to [Fe(cp)(CO),]+ and their co-ordination is rare for other metal-containing fragments.Isolated examples include [Fe(CO),( MeOOC(H)C=C-(COOMe), )I8 and rhodium complexes of a-amidoacrylic acidsfor which the alkene co-ordination is stabilised by co-ordinationof the amido oxygen atom to form a chelate ring.'During the course of studies aimed at the co-ordination oftrisubstituted alkenes to transition elements,lO we haveinvestigated reactions of [Fe(cp)(CO),Cl] with 3-methylbut-2-enoic acid and its methyl ester.We now report the results ofthese investigations.t Present address: Chemistry Department, University of St. Andrews,St. Andrews, Fife KY16 9ST.$ Supplementary data available (No. SUP 56483, 5 pp.): H-atom co-ordinates, thermal parameters. See Instructions for Authors, J. Chem.SOC.. Dalton Trans., 1986, Issue 1, pp. xvii-xx. Structure factors areavailable from the editorial office.Results and DiscussionReaction of [Fe(cp)(CO),CI] with AgSbF, in the presence ofMe,WHCOOH (molar ratio, 1 : 1 : 1) leads to the productionof two complexes, one orange and the other red.The orangecomplex, which is obtained from reactions carried out inmethanol-dichloromethane (1 : l), has the formula [(Fe(cp)-(CO),(Me,C=CHCOO)),H][SbF,] and is sufficiently stablefor crystallisation, whilst the red complex, which has the stoi-cheiometry [Fe(cp)(C0),(Me,GCHCOOH)][SbF6], is un-stable in solution and readily releases the acid in non-polarsolvents. In dichloromethane a slow reaction with the solventoccurs to give the known complex' '.12 [(Fe(cp)(CO),),Cl]-[SbF,], for which the X-ray crystal structure is described below.The complex [Fe(cp)(CO),Cl] also reacts with AgSbF, inthe presence of Me,C=CHCOOMe to give an oily red solidwhich is difficult to crystallise and is substitution labile in polarsolvents.This complex is apparently of formula [Fe(cp)(CO),-(Me,GCHCOOMe)][SbF,].These complexes have been characterised by spectroscopicmeans (see Tables 1 and 2) and the X-ray crystal structure of[ (Fe(cp)(CO),(Me,C=CHCOO)),H][SbF,] has been deter-mined.Structure of [ (Fe(cp)(CO),( Me,C=CHCOO)} H][SbF6].-The structure of [(Fe(cp)(CO),(Me,C=CHCOO)},H] + isshown in Figure 1, and selected bond angles are in Table 3. Thetwo Fe(cp)(CO),(Me,C=CHCOO) units are linked across acentre of symmetry at 0.25, 0.75, 0.5 by a hydrogen-bondedhydrogen atom. This hydrogen atom, which has been identifiedby a peak in the electron-density map, may be symmetricallybonded to the two oxygen atoms or may be asymmetricall1130 J.CHEM. SOC. DALTON TRANS. 1986Table 1. Infrared data (em-') for new iron complexes and their parent alkenesCompound v(O-H) V(Cz0) V(C=o) V(C=c)Me,C=€HCOOH 3 lOOvbr - 16% 163OvsMe,C=CHCOOMe - - 1 72Ovs, br 1 655vs, br[ Fe(cp)(CO),( Me,WHCOOH)] [SbF,] 3 3oOm, br 2 06ovs, 2 Ol5vs 1 665s 1625s[{Fe(cp)(CO),(Me,C=CHCOO)},H][SbF,] 1 72Ow, vbr 2 052vs, 2 007vs 1 61Om, br 1 645m, br[ Fe(cp)(CO),( Me,C=CHCOOMe)][SbF,] - 20754, 2020vs 1 595s 1640s, brTable 2. Proton n.m.r. data for iron complexes and their organic precursors in CD,CI, at 25 OC*Compound CP Me, Me, HC OR J(HaHc)IHz J(H,HC)IHzMe,C=CHCOOH - 1.98(d) 2.23(d) 5.78(m) 12.11(br s) 0.8 1.5Me,C=CHCOOMe - 1.90(d) 2.17(d) 5.66(m) 3.64(s) 1 .o 1.5[ Fe(cp)( CO),( Me,C=CHCOOH)] [ S bF6] 5.21(s) 1.95(s) 1.95(s) 5.74(s) 9.76(br s) 0 0[(Fe(cp)(C0),(Me,C=CHCOO)~,H][SbF6] 5.16(s) 1.81(s) 1.87(s) 5.56(s) 9.26(br s) 0 0[Fe(cp)(CO),(Me,C=CHCOOMe)][SbF,] 5.29(s) 1.99(s) 2.06(s) 5.58(s) 3.82(s) 0 0* For assignments, .see Figures 2 and 3.T a b 3.Selected bond lengths (A) and angles (") for [{Fe(cp)-(CO),(Me,C=CHCOO)} ,H][SbF,]Fe( 1 )-cp(av.) 1.708 C(10)-C(11) 1.463(11)Fe( 1 W ( 6 ) 1.774( 10) C( 10)-O( 8) 1.238(9)Fe( 1 W ( 7 ) 1.777(11) C( lOW(9) 1.283(10)Fe( 1 W ( 8 ) 1.965(6) C(11WU2) 1.3 18( 12)C(6W(6) 1.125( 14) C( 12)-C( 13) 1.497( 15)C(7t-0(7) 1.123( 15) C( 12)-C( 14) 1.5 18( 15)Sb-F(av.) 1.785 O(9) * O(9') 2.406(9)92.9(5)96.1(4)97.1(4)175.7(10)174.8( 10)12645)123.0122.0120.1122.7(7)117.2(7)120.0(7)128.2(8)125.2(9)119.2(8)1 15.6(9)180.0(4)Figure 1.Solid-state structure and numbering scheme for [{ Fe(cp)-(CO),(Me,C=CHCOO)) ,HI+Table 4. Selected dihedral angles (") for [{ Fe(cp)(CO),(Me,C=CHCOO)) ,HI [SbF,]2.30(14)- 179.90(9)- 178.00(6)4.20( 1 0)1.10(15)179.50(9)180.00(7)179.43(6)1.53(9)bound. In the latter case, the crystallographic centre ofsymmetry would arise from disorder of this hydrogen atomthroughout the crystal.have shownthat, in general, unsymmetrical hydrogen bonds lead to adistance between the two hydrogen-bonded oxygen atoms of ca.2.6-2.7 A, whilst a shorter distance (ca. 2.5 A) is observed forsymmetrical hydrogen bonds.The O(9) O(9') distanceobserved in [(Fe(cp)(CO),(Me,C=CHCOO)),H] + is 2.406(9)A, consistent with there being a symmetrical hydrogen bond,and the i.r. spectroscopic data are consistent with thissuggestion. Such symmetrical hydrogen bonds are not un-common and examples where carboxylate anions are hydrogenbonded in this way are well known.13 However, we believe[(Fe(cp)(CO),(Me2CHCOO)),H1 + to be the first exampleof a complexed carboxylate ion to be hydrogen bonded in thisway. The related [(Fe(cp)(CO) (PPhBu'O)),H][BPh,] withan 0 0 distance of 2.4O3(4) 8: has been crystallographicallycharacterised.The (Me,C=CHCOO),H unit is essentially planar, withdihedral angles as shown in Table 4. The bond lengths withinthis unit are comparable with those found for but-2-enoic acidand but-2-enamide (Table 9,'' both of which crystallise ashydrogen-bonded dimers, consistent with substantial delocalis-ation of the electrons in the 'IC system.This is reflected by theshort C( lO)-C( 11) bond [ 1.463( 11) A, cJ: 1.54 for a normalC-C single bond]. The lengths of the C=O bonds in [(Fe-(c~)(CO),(M~,C=CHCOO)}~H] + [ 1.238(9) A] are shorterthan in but-2-enoic acid [1.265(9) A], where the hydrogen bondis asymmetric, but are similar to those found in e.g. Na-[(MeCOO),H] (1.243 A)16 or potassium chloromaleate(1- )(1.226, 1.240 A)*' both of which contain short, probablysymmetrical hydrogen bonds. Apparently the effect of co-Studies on other hydrogen-bonded speciesJ. CHEM.soc. DALTON TRANS. 1986 1131Table 5. Bond lengths (A) for [{FC(~~)(CO)~(M~~GCH-C00))2H J[SbF6] (l), butcnoic acid, and butenamide compared with'normal' lengths of isolated bondsButenoic Normal(1) acid Butenamide bond lengthC(11)4(12) 1.318(12) 1.293(11) 1.326(7) 1.33C(10)4(11) 1.463(11) 1.459(9) 1.502(6) 1.54C(10)-0(8) 1.238(9) 1.265(9) 1.221(5) 1.21C( 10)-0(9) 1.283( 10) 1.287(9) - 1.30C(12)-c(14) 1.518(15) 1.5039) 1.491(7) 1.540' \Figure 2. Diagrammatic representation of the bonding in the [(Me,=CHCOO),H] - unit of [(Fe(cpNCO),(Me,C=CHCOo)),HI +ordination of the carbonyl group to the iron is little differentfrom the effect of non-bonded interactions with alkali-metalatoms in the other salts containing short hydrogen bonds.' 6* ' 'Despite this delocalisation the structure is best described asconsisting of [(Me,C=CHCOO),H] - co-ordinated via thecarbonyl oxygen atoms to two [Fe(cp)(CO),]+ units and thedelocalisation probably allows some charge neutralisation(Figure 2).The remainder of the structure of the cation is notunusual and the only other feature of note is that each SbF6- issurrounded by eight cyclopentadienyl groups which form aspherically symmetrical cavity. The presence of the sphericallysymmetrical anion in this cavity probably contributes to therotational disorder observed for this anion.Spectroscopic Properties of the Complexes.-Importantfeatures of the i.r. spectra of Me,WHCOOR (R = Me or H)and of their complexes with [Fe(cp)(CO),] + are listed in Table1. In all cases, v(C=O) and v ( W ) are clearly visible near 1 600cm-'. It is possible, on the basis of studies carried out usingrhodium complexes of the diphenylphosphinous ester, Ph2P0,-CCHSMe,," to correlate the position of v(C=O) and v ( W )with the bonding mode of the acrylate group.Thus, for[(RhC1(Ph,P02CCH=CMe2)}2], which has been showncrystallographically to have binding via C=C, v(C=O) appearsto higher frequency than for the free acid (1 690 cm-') andv(C=C) is not observed above 1 550 cm-', whilst, where bindingis through the carbonyr oxygen, as in [Rh(PPh3),(Ph2-PO,CCH=CMe,)]+, v(=) is at 1640 cm-I and v(C--O) isshifted to lower frequency (1 585 cm-I).The similarity in the values of v(C=O) and v(C=C) for[Fe(cp)(CO),(Me,CHCOOH)] + and for the free acidclearly suggest that the R system of the acid is disturbed verylittle on bonding to the metal and hence that bonding isprobably through the OH oxygen atom of the acid, as in Figure3(a).For this complex v(O-H) is observed as a medium broadband at 3 300 cm-', suggesting a small amount of hydrogenbonding perhaps to the carbonyl oxygen atom of anotherbound acid [Figure 3(a)].Me \MeFigare 3. Proposed structure for [Fe(cp)(CO),(Me,C=CHCOOR)] +where R = H (a) or Me (b)The slightly lower values of v(C=O) and v ( W ) observed for[{ Fe(cp)(CO),(Me,<==CHCOO)} ,HI + are consistent with theobserved delocalisation of the R system in the molecule (seeabove) and with binding through the carbonyl oxygen atom,whilst the failure to observe v(0-H) near 3000 cm-' isconsistent with there being a symmetrical hydrogen bond.Compounds which contain symmetrical hydrogen bondsgenerally exhibit variable positions for v(0-H) and, on the basisof previously observed correlations,'* an 0 0 distance of2.41 A should give v(O-H) at 1 700-1 800 cm-'.A broad weakfeature centred at 1 720 cm-' but overlapping with v ( M ) istentatively assigned to v(O-H) for this complex.Finally, for [Fe(cp)(CO),(Me,G€HCOOMe)] + the twoabsorptions near 1 600 cm-' are substantially shifted from theirpositions in the free ester. We assume that this indicates bindingthrough the carbonyl oxygen atom of the ester group [Figure3(6)], and tentatively assign v(G0) at 1 595 cm-' and v(GC)at 1 64ocm-'.The intensity of v ( W ) for the free and bound acid and esteris much greater than is normally observed for unsymmetricalalkenes.This suggests that some intensity borrowing fromv(C=O), probably via Fermi resonance, is occurring. In all cases,there is probably substantial mixing of the two vibrations.The 'H n.m.r. spectra of the three complexes are unexcep-tional (Table 2) and the high value of 6 for the vinylic protonin each case is consistent with there being no metal-alkenetype interaction. For [Fe(cp)(CO),(Me,C=CHCOOH)] + ,although the spectrum in CD,Cl2 is complicated by thepresence of free Me,GCHCOOH and presumably [(Fe(cp)-(CO)2}2Cl]+, the methyl resonances of the bound acid appearto give a single resonance, presumably on account of anaccidental degeneracy. The lability of [Fe(cp)(CO),-(Me,C=CHCOOMe)] + is confirmed by the observation that'H n.m.r.spectra measured in C2H6]acetone (solv) show only acyclopentadienyl resonance {presumably from [ Fe(cp)(CO),-(solv)] +) and resonances from free Me,GCHCOOMe.The fast atom bombardment mass spectrum of [{Fe(cp)-(co),(Me,cl=cHCoo)),H][SbF,] in a matrix of 3-nitro-benzyl alcohol shows a signal of medium intensity atm/z 553 corresponding to the parent ion, [{Fe(cp)(CO),-(Me,WHCOO)} ,HI +, and fragments corresponding toCFe(cp)(CO),(Me2C=CHCOOH)I + , CFe(cp)(CO)(Me,C1132 J. CHEM. soc. DALTON TRANS. 1986Tabk 6. Selected bond lengths (A) and angles (") for [(Fe(cp)-(CO), ~2CIICSbF61Fe( 1 )-Cl 2.309(4) Fe(2)-CI 2.306(3)Fe( f W(6) 1.773(8) Fe(2)-C( 1 6) 1.8 1 O( 1 0)Fe( 1 W(7) 1.774(8) Fe(2)-C( 17) 1.7839)Fe( 1 )-cp( l)(av.) 1.71 5 Fe(2)-cp(Z)(av.) 1.704C(6)-0( 1 ) 1.152( 10) C(16)-0(11) 1.110(12)C(7)-0(2) 1.146(9) C( 17)-O(21) 1.135( 10)Sb( 1 )-F(av.) 1.841cp(1)-Fe(l)-Cl(av.) 123.0cp(l)-Fe(l)-C(7)(av.) 122.8cp( I)-Fe( 1 )-C(6Xav.) 121.8Fe( 1 )-C(~)-cy 1) 1 79.1 (5)Fe( 1 )-C(7W(2) 17837)C(7kFe(l)-C(6) 9334)C(6)-Fe( 1 )-CI 95.9(3)C(7FFdlW 92.2(3)Fe( 1 )-CI-Fe( 2) 1 19.4(2)cp(2)-Fe(Z)-Cl(av.) 122.9cp(2)-Fe(2)-C( 17)(av.) 122.4cp(2)-Fe(2)-C( 16)(av.) 124.0Fe(Z)-C( 16)-O( 1 1) 177.0(6)Fe(2)-C( 17)-0(21) 177.6(2)C( 17)-Fe(2)-C( 16) 93.9(4)C( 16)-Fe(2)-C1 94.7( 1 )C( 17)-Fe(2)-CI 9043)O(2)Figure 4. Solid-state structure and numbering scheme for [(Fe(cp)-(CO),) K11+CHCOOH)]+, and [Fe(cp)(Me,C==CHCOOH)] + at m/z 277,249, and 221 respectively.The peaks at m/z 277 and 221 werevery intense compared with the rest of the spectrum.Structure of [{ Fe(cp)(CO),},C1][SbF6].-The structure of[{Fe(cp)(CO),},Cl]+ is shown in Figure 4 and selected bondlengths and angles in Table 6. The complex contains twoFe(cp)(CO), units bridged by a chlorine atom, the angle atchlorine being 119.4(2)". The structure of this cation is similar tothat of [ Fe(cp)(CO),),I]+, where the angle at iodine is1 10.8(1)"." The rather larger angle at chlorine than at iodine isprobably caused by steric repulsions between the twoFe(cp)(CO), units, which will be higher in the case of the chloro-bridged dimer on account of the smaller covalent radius ofchlorine. The Fe(cp)(CO), groups have similar parameters tothose in [{Fe(cp)(CO),(Me,C=CHCOO)),H]~ and are un-exceptional.The fluorine atoms of the SbF6- ions aredisordered with approximately half occupancy of two isomersrelated by a 30" rotation about a local C , axis of the octahedron.ExperimentalMicroanalyses were by Elemental Micro-Analysis Ltd. 1.r.spectra were obtained on a Perkin-Elmer 577 grating spectro-meter using Nujol mulls between caesium iodide plates, 'Hn.m.r. spectra on Perkin-Elmer R12B (60 MHz) or BrukerWM25O (250 MHz) spectrometers, and mass spectra on a V G7070E spectrometer. Standard Schlenk-line and catheter-tubingtechniques were employed, and all solvents were carefully driedby distillation from CaH, (CH,Cl,), sodium diphenylketyl[diethyl ether, light petroleum (b.p.40-60 "C)], or magnesiummethoxide (methanol) before use.3- Methyl bu t-2-enoic acid (Aldrich) was recrys tallised beforeuse and AgSbF, was stored over phosphorus pentoxide. Thecomplex [Fe(~p)(C0),Cl]'~ and Me,C=CHCOOMe were pre-pared by standard methods.Dicarbonyf(~-cycfopentadienyf)(3-methyfbut-2-enoic acid)-iron(I1) HexaJluoroantimonate.-Dichloromethane (30 cm')was added to a mixture of [Fe(cp)(CO),Cl] (0.302 g, 1.42 mmol)and AgSbF, (0.488 g, 1.42 mmol) and the mixture was stirredfor 5 min to give a deep red solution and a white precipitate. Theacid Me,C=CHCOOH (0.142 g, 1.42 mmol) in CH,Cl, (20 cm')was added and the mixture was stirred for 0.5 h before filtration,concentration to ca.10 cm', and cooling to -20 "C. Diethylether was added until a red solid began to precipitate and after0.5 h at -20 "C it was collected, washed with diethyl ether at- 20 "C, and dried in vucuo. Yield 0.23 g (32%) (Found: C, 28.2;H, 2.45. C ,H ,F,FeO,Sb requires C, 28.1; H, 2.4%).Bis[dicarbonyf(q-cycfopentadienyf )( 3-methyfbut-2-enoato)-iron ( I I)] hydrogen HexaJuor oan t imona t e.-Dic hlo rome t hane(20 cm') was added to a mixture of [Fe(cp)(CO),Cl] (0.699 g,3.3 mmol) and Me,C=CHCOOH (0.329 g, 3.3 mmol). Afterstirring for 1 min, AgSbF, (1.128 g, 3.3 mmol) in CH,Cl, (30cm3) was added and the solution stirred for 0.5 h. The darkorange solution was filtered from the precipitated AgCl and thesolvent was evaporated to ca.20 cm'. Methanol (10 cm3) wasadded and the volume of solvent was reduced by evaporation toca. 15 cm'. On standing a bright orange microcrystallinematerial precipitated (0.24 g). Cooling of the mother-liquorgave a crop of orange plates (0.134 g). Combined yield 0.37 g(28%) (Found: C, 34.45; H, 3.10. C,,H,,F6Fe2O,Sb.O.5CH,-C1, requires C, 35.45; H, 3.20%). The presence of 0.5 molCH,Cl, per mol of complex cation was confirmed by 'H n.m.r.spectroscopy .Dicarbonyl(q-cycfopentadienyf)(methyf 3-methyfbut-2-eno-ate)iron(n) HexaJluorantimonate.-Dichloromethane (25 cm3)was added to a mixture of [Fe(cp)(CO),Cl] (0.5 g, 2.3 mmol)and AgSbF, (0.80 g, 2.3 mmol). After stirring for 10 minMe,C=CHCOOMe (0.26 g, 2.3 mmol) in CH,Cl, was addedand the solution stirred for 0.5 h.The red solution was filteredfrom precipitated AgCl and treated with light petroleum (20cm3). The red oil was collected, washed with light petroleum(2 x 10 cm3), and recrystallised from CH,Cl,-diethyl ether at-20 "C to give an oily solid. This was collected, washed withdiethyl ether, and dried in uucuo. Yield 0.4 g (33%) (Found: C,26.3; H, 2.9; F, 22.7. C,,H,,F,FeO,Sb requires C, 29.6; H, 2.9;F, 2 1.6%).Decomposition of [Fe(cp)(CO),( Me,C=CHCOOH)] [S bF,]in Dichforomethane.-The complex [ Fe(cp)(CO) ,(Me,=CHCOOH)][SbF,] (0.1 g) was dissolved in CH,Cl, (5 cm').After filtration, the solution was stored at -25 "C for severaldays. The dark red crystals which separated were collected anddried in air. Yield of [{Fe(cp)(Co),),C1][sbF6] 0.03 g (49%)(Found: C, 27.4; H, 1.75. CI,Hl,ClF,Fe204Sb requires C, 26.9;H, 1.6%).Crystaffography.-[ { Fe(cp)(CO),( Me,C<HCOO)) , HI-[SbF,].Thin platy crystals were obtained from chlorobenzene-light petroleum at - 20 "CJ. CHEM. soc. DALTON TRANS. 1986 1133Table 7. Atom co-ordinates ( x lo4)Atom X Y zSb 0) W1) 2 W O )(a) [ { Fe(cp)(CO) 2 (Me2 C ~ H c O o ) } 2 1 Cs bF61F(1) O(0) 2 516(11) 2 500(0)F(3) - 74(6) 91(12) 3 720(6)F(4) -573(4) 108(17) 2 015(12)Fe(1) 1 118(0) 6015(1) 5006(1)C(1) 668(3) 5 623( 13) 5 952(7)H(1) 71O(3) 6 184(13) 6 674(7)C(2) 448(3) 6 442( 13) 5 102(8)H(2) 289(3) 7 742( 13) 5 052(8)(33) 468(3) 5 306(14) 4 335(7)H(3) 325(3) 5 556(14) 3 58O(7)C(4) 71O(3) 3 742(12) 4 715(7)W4) 788(3) 2 607( 12) 4 300(7)F(2) O(0) -2 369(12) 2 sOo(0)(b) [{ Fe(cp)(Co)2} 2C11[SbF61Fe(1) 1511(1) 1878(1)Fe(2) 4490(1) 2 37O(1)CI 3 252(1) 1 899(1)0 ( 1 ) 1721(4) 3 320(4)O(2) 1007(5) 3665(4)O(11) 3 6 4 q 5 ) 1009(5)O(12) 5 910(4) 693(4)C(1) 34(5) 1231(6)C(2) 43O(5) 1020(5)C(3) 1319(5) 404(6)C(4) 1468(5) 1 72( 5 )C(5) 686(5) 709(6)C(6) 1646(4) 2754(5)C(7) 1 211(4) 2 956(5)C(11) 4 119(5) 4000(4)C(12) 5 106(5) 3 743(5)C( 13) 5 770(5) 3 395(5)4 03O(1)6 043( 1)4 271(1)5 971(5)2 369(5)7 W5)5 842(7)3 268(6)4 4w6)4 757(7)3 695(8)2 790(6)5 208(5)3 013(5)5 641(6)5 575(6)6 656(7)X826( 3)1 o w 3 )1255(3)1314(3)1245(3)1293(3)2 088(2)2 51 l(3)2 821(3)2 561(3)2 180(4)3 037(4)I 708(2)2 123(2)5 236(6)4 198(5)3 959(5)5 349(4)7 994(.5)7 950( 5 )8 147(7)8 986(8)6 846(8)8 822(8)7 023(8)7 809(9)7 873(9)9 372(8)6 527(7)9 360(10)7 826(8)Y3 945(12)2 985(12)6 410(15)6 67O( 15)8 246(13)9 688(10)5 536(10)4 637( 1 1)5 290(11)3 134(12)1 993(16)2 437( 16)4 969(7)6 999(8)3 401(6)3 824(5)1 505(5)1 346(5)3 290(.5)2 086( 5 )4 586(6)2 510(9)3 824(8)4 o(w9)2 509( 10)4 020(9)4 190(10)2 966( 10)3 369(9)3 365(10)2 536(10)z5 715(7)6 220(7)3 845(7)3 087(5)5 393(9)5 W(9)5 508(6)5 944(6)5 848(6)6 441(6)6 651(10)6 822(8)5 589(4)5 052(5)7 404(7)6 777(7)6 864(6)5 895(7)4 639(.5)3 746(6)5 479(8)5 382(9)3 489(9)4 031(10)5 021(10)3 364(10)5 711(11)5 623( 12)4 098(10)4 872( 13)5 898(10)Crystaldata. C,,H,,F,Fe,08Sb, M = 789, monoclinic, a =29.901(2), b = 7.495(2), c = 14.006(2) A, p = 100.65(1)", U =3 084.62 A3, F(0oO) = 1 560, space group C2/c, D, = 1.667 g~ m - ~ , 2 = 4, D, = 1.699 g ~ m - ~ , Mo-K, radiation, h = 0.710 7A, p = 18.73 cm-'.Intensity data were recorded on a CAD4 diffractometer bymeasuring in four octants of reciprocal space to Om,,.= 25".These were merged to give 2 713 unique reflections andcorrected for absorption empirically. The structure was solvedby Patterson and Fourier methods. The positions andanisotropic vibrational parameters of all non-hydrogen atomswere refined. Hydrogen atoms in the cyclopentadienyl groupand on C( 1 1) were included in the structure-factor calculation(one isotropic vibrational parameter employed for all hydrogenatoms).The final R factor was 0.049 for 1 972 reflections withF > 2.5cr(F). The largest peaks in the final difference map were0.5-1 e A-3 in the vicinity of the SbF6- and Fe atom. A peak of0.3 e appeared at the centre of symmetry between O(9) and0(9'), 2.41 A apart. In Figure 1, this has been included as ahydrogen atom, H(9).The SbF6- group lies on a two-fold axis and the Sb-F andF-F distances were constrained to correspond to octahedralgeometry; some of the anisotropic vibrational parametersderived by least-squares refinement are unrealistically large andmust imply some orientational disorder of the anion.However,the final difference map shows that these vibrational parametersprovide an adequate model for the electron density in thisregion. Some other atoms, notably the carbonyl oxygen atoms,C( 13), and O(9) also have very anisotropic vibrational para-meters suggesting that there may also be some disorder inthese regions. The fractional co-ordinates are in Table 7.Computations were made using the program SHELX 76 ' onan IBM 4341 comwter.[(Fe(cp)(CO),},Cl][SbF6]. Crystal data. c i4H &IF6-Fe,O,Sb, M = 625, monoclinic, a = 13.805(4), b = 12.301(3),2.11 g ~ m - ~ , F(0oO) = 1200, space group P2,/c, Mo-K,radiation, h = 0.710 69 A, p(Mo-K,) = 30.2 cm-*.A total of 6 412 intensity data were measured with 5 707unique and 4 540 with I > lScr(1).Final R values were R =0.053 and R' = [Z(WA)~/AWF,~]+ = 0.065.,,Preliminary cell dimensions were obtained from photographsand refined using the setting angles for 25 reflectionsautomatically determined on an Enraf-Nonius CAD4 diffracto-meter. Intensities were collected with nickel-filtered Mo-K,radiation in the -20 scan mode. The structure was solved viathe heavy-atom method and refined by full-matrix least squares.All non-hydrogen atoms were located in a difference map andassigned anisotropic thermal parameters. Twelve sites werelocated for fluorine atoms around the antimony atom whichafter refinement were fixed at half occupancy. Hydrogen atomswere located experimentally and refined with isotropic thermalparameters.The fractional co-ordinates are in Table 7.Computations were made using the program SHELX 76 2 1 ona DEC VAX 11/750 computer. An absorption correctionwas performed using the program DIFABS.,,c = 12.457(3)A, fl = 111.88(2)", U = 1963.1 A3, 2 = 4, D, =AcknowledgementsWe thank the S.E.R.C. for a Studentship (to D. C. C.), thepurchase of the high-field n.m.r. machine, and other support o1134 J. CHEM. soc. DALTON TRANS. 1986the X-ray work. D. J. C-H. is Sir Edward Frankland Fellow ofthe Royal Society of Chemistry, 1984-1985.References1 W. P. Giering and M. Rosenblum, J. Orgunomet. Chem., 1970, 25,2 W. P. Giering and M. Rosenblum, Chem. Commun., 1971,441.3 A. Cutler, D. Ehntholt, W. P. Giering, P. Lennon, S. Raghu, A.Rosan, M. Rosenblum, J. Tancrede, and D. Wells, J. Am. Chem. SOC.,1976,s. 3495.C71.4 K. Nicholas and M. Rosan, J. Organomet. Chew., 1975, 84, 351.5 D. F. Marten, J. Chem. SOC., Chem. Commun., 1980, 341.6 B. M. Foxman, J, Chem. Soc.. Chem. Commun., 1975,221.7 D. E. Laycock, J. Hartgerink, and M. C. Baird, J. Org. Chem., 1980,45, 291.8 T-A. Mitsudo, H. Nakanishi, T. Inubishi, I. Morishima, Y.Watanabe, and T. Takegami, J. Chem. SOC., Chem. Commun., 1976,416.9 J. Halpern, Pure Appl. Chem., 1983, 55, 99 and refs. therein.10 D. Cupertino, M. M. Harding, and D. J. Cole-Hamilton,unpublished work.11 W. R. Cullen, D. J. Patmore, and J. R. Sams, Inorg. Chem., 1973,12,867.12 D. A. Symon and T. C. Waddington, J. Chem. SOC., Dalton Trans.,1974, 78.13 J. C. Speakman, in ‘Molecular Structure by Dilfraction Methods,’eds. G. A. Sim and L. E. Sutton, Specialist Periodical Report, TheChemical Society, London, 1975, vol. 3, p. 86 and refs. therein.14 P. M. Treichel and L. D. Rosenhein, Inorg. Chem., 1981,20, 1539.15 S. Shimuzu, S. Kekka, S. Kashino, and M. Haisa, Bull. Chem. SOC.16 M. J. Barrow, M. Currie, K. W. Muir, J. C. Speakman, and D. N. J.17 R. D. Ellison and H. A. Levy, Acta Crystallogr., 1965, 19, 260.18 G. C. Pimentel and A. L. McClellan, ‘The Hydrogen Bond,’19 F. A. Cotton, B. A. Frenz, and A. J. White, J. Organomet. Chem.,20 E. 0. Fischer and E. Moser, Inorg. Synth., 1970, 12, 35.21 G. M. Sheldrick, ‘Computing in Crystallography,’ Dclft University22 N. Walker and D. Stuart, Acra Crystallogr., Sect A , 1983,s. 158.Jpn., 1974, 47, 1627.White, J. Chem. SOC., Perkin Trans. 2, 1975, 15.Freeman, New York, 1960 and refs. therein.1973,60, 147.Press, Delft, Holland, 1978, p. 34.Received 29th July 1985; Paper 5/130

ISSN:1477-9226    

DOI:10.1039/DT9860001129

出版商:RSC    

年代:1986

数据来源: RSC