摘要:
J. CHEM. SOC. DALTON TRANS. 1982 2221Pentakis( methoxycarbony1)cyclopentadiene Chemistry. Part 2.'Some Derivatives containing the Alkaline-earth Metals (Mg, Ca, Sr,or Ba) or Group 2 Metals (Zn or Cd). Crystal and MolecularStructure of Ba[Cs(C02Me)s]2 tMichael 1. Bruce" and Jennifer K. WaltonDepartment of Physical and Inorganic Chemistry, University of Adelaide, South Australia 500 7Brian W. Skelton and Allan H. White *Department of Physical and Inorganic Chemistry, University of Western Australia, Nedlands,Western Australia 6009White, air-stable, and water-soluble compounds M [C5(C02Me)5]2 (M= Mg, Ca, Sr, Ba, Zn, and Cd) areobtained from HC5(C02Me)5 and the metal carbonates or acetates, or from MC12 and TI[C5(C02Me),] ;the i.r., H n.m.r., and mass spectra are reported and briefly discussed.The structure of the barium derivativehas been determined at 295 K by single-crystal X-ray diffraction methods, and-refined to a residualof 0.036 for 8 173 ' observed ' reflections. Crystals are triclinic, space group P1, with a = 14.499(4),b = 12.940(4), c = 10.745(2) A, a = 100.54(2), p = 100.02(2), y = 114.23(2)", and Z = 2. Thebarium atom is eight-co-ordinate with an environment made up of three pairs of chelatingcarboxyl-carbonyl oxygen atoms and two others [Ba-0 2.655(3)-2.932(3) A] ; as in the alkali-metalderivatives, there is a tendency for adjacent carboxyl-carbonyl groups to behave as chelate functions.In the previous paper we described the preparation andproperties of alkali-metal and thallium(1) derivatives of thestrong organic acid pentakis(methoxycarbony1)cyclopenta-diene, HC5(C02Me)5 (Hpmcp).We showed how the presenceof the five strongly electron-withdrawing substituents resultedin the formation of air-stable, water-soluble compounds, andX-ray crystal-structure studies of some demonstrated thepreference for oxygen co-ordination to the hard metal ions.In this account, we report on some derivatives of bivalentmetal ions of Groups 2A and 2B.Results and DiscussionIonic complexes of the type M(pmcp), [M = Mg (l), Ca (2),Sr (3), Ba (4), Zn (3, or Cd (6)] have been prepared fromreactions of the diene with metal carbonates or acetates[equations (i) and (ii)], or from the metal chloride and thethallium(1) salt [equation (iii)].The compounds so obtainedHa0 MC03 + 2Hpmcp -M(02CMe), + 2Hpmcp ___tW P ~ C P ) ~ + H2O + C o d - (i)M(pmcp), + 2MeC02H (ii)(iii)MeOHMeOHMC& 3- 2TKpmcp) - M(pm~p)~ + 2TlCI J.have been characterised by elemental microanalyses, conduc-tivity measurements, and from their spectroscopic data. Theanalyses are consistent with the formulation M(pmcp)2 for M= Ca, Ba, or Sr; the magnesium complex is a monohydrate,while the strontium and zinc derivatives are trihydrates. Thelast two compounds could not be dehydrated by heating at100 "C in vucuo for 8 h. All compounds are air-stable whitesolids, soluble in water, which if anhydrous melt above 300 "C;the hydrates have considerably lower melting points. Inaqueous solution, molar conductances range between 130 and1- Supplementary data available (No.SUP 23353, 30 pp.): thermalparameters, methyl H-atom parameters, structure-factor ampli-tudes. See Notices to Authors No. 7, J. Chem. Soc., Dalton Trans.,1981, Index issue.160 ohm-' cm2 mol-', values expected for 2 : 1 electrolytes,and clearly indicating their ionic nature.The i.r. spectra (Table 1) all show several strong v(C=O)absorptions above 1 600 cm-', and v(C0) bands close to 1 200cm-'. Although complex, the spectra are similar to that of thepotassium salt, in which several of the ester carbonyl groupsare involved in weak co-ordination of the metal ion. Anadditional feature of the spectra of the hydrated derivatives isa broad v(0H) absorption at ca. 3 350 cm-'. The 'H n.m.r.spectra of solutions in D20 each contains a single resonancebetween 6 4.28 and 4.51 assigned to the methoxy-protons ofsymmetrical [C5(C02Me)5]- anions.In (CD3),C0 this reson-ance has shifted to 6 3.68. The mass spectra of Ca(pmcp), andZn(pm~p)~ contain only ions formed by the breakdown of[C5(C02Me)5]+ (m/e 355); no molecular ion was observed, asis common for ionic compounds.Although the properties of these compounds suggest thatthe pmcp ligands are 0-bonded to the metal ions, probably bypairs of ester carbonyl groups acting as chelate functions, theprecise structure could not be established. Accordingly wehave carried out a single-crystal X-ray study of the bariumderivative (4).Structure of Ba[C5(C02Me)5]2 (4).-The unit-cell contents(Figure) agree with the expected stoicheiometry Ba[C5-(C02Me)5]2, one formula unit comprising the asymmetric unit.The Ba is eight-co-ordinate with Ba-0 distances rangingfrom 2.655(3) to 2.932(3) A (average 2.76 A).There are fewcompounds with which to make any comparisons of similarBa-0 bond lengths, but those in (4) appear to be shorterthan most. For example, in four complexes containingmacrocyclic polyethers, mean Ba-0 distances are found to bein the range 2.82-2.93 A;' other values of 2.82 in Ba(02CH)2,32.87 in BaC204*2H20,4 and 2.96 A in BaC204.H2C204.2H20 have also been reported. Only those in Ba(O,CMe),-[N(CH2CH20H)3]2 [range 2.743-2.805(4), average 2.767 A]and Ba(SCN)2(C14H28N204) (Cl4HZ8N2O4 =4,7,13,18-tetra-oxa- I , I O-diazabicyclo[8.5.5]icosane) ' [range 2.747-2.824( 7),average 2.783 A] are similar to those in (4).All of the eight-co-ordinated oxygen atoms are of typeO(nl), i.e.the carbonyl oxygens. Of these, three pairs aredrawn from adjacent substituents in the ligands and thu2222 J . CHEM. SOC. DALTON TRANS. 1982Table 1. Infrared spectra (cm-') of M(pmcp), obtained from Nujol mullsSignificant bandsv(C=O) 1750m, 1729m, 1 703 (sh),1696s, 1674s, 1 646mv(C-0) 1 315s, 1 288m, 1 266s,1 203sv(C=O) 1733s, 1 704s, 1 684vs,1615vsv(C-0) 1 310~, 1290~, 1252~, 1200sv(0H) 3 620m, 3 545m, 3 485m,3 420mv(C=O) 1 760-1 650vs (vbr)v(C-0) 1297s, 1 220s (br)v(C=O) 1 705s, 1 700 (sh), 1 689s,1 664 (sh), 1 657 (sh), 1 653s, 1 646sv(C-0) 1293~, 1 23&, 1209sv(0H) 3 440111, 3 355m (br)v(C=O) 1750m, 1709s, 1 687m,1 660sv(C-0) 1 313m, 1279m, 1 236s,1 215m, 1 200sv(C=O) 1 732m, 1707m, 1 688 (sh),1 674s, 1 657 (sh), 1 650s, 1 635wv(C-0) 1312m, 1289m, 1254s,1 202sOther bands1445w, 1428m, 1417w, 1 368m, 1 180m, 1088m, 1071m, 1008m, 987w,964w, 946 (sh), 941w, 894w, 874vw, 863w, 840w, 818w, 790m, 766m, 751m,720w, 703w, 678w1428m, 1418m, 1408w, 1 367m, 1 178s, 1085m, 1071m, 1006m, 991m,960w, 942m, 889m, 866w, 857vw, 848w, 817w, 789m, 768m, 750m, 721w,703w, 678w1485 (sh), 1 420w, 1 408w, 1 368 (sh), 1 178s, 1 087m, 1070m, 1008m,987m, 965w, 944m, 885w, MOW, 869vw, 858w, 836m, 810vw, 795 (sh),791m, 781w, 759m, 750w, 721w, 701w, 678w1419w, 1403w, 1 368w, 1 178s, 1076m, 1007m, 984w, 940w, 880w, 860w,848w, 806vw, 793w, 785w, 763w,,753m, 721w, 695w1 460 (sh), 1 430 (sh), 1 420w, 1404w, 1 368 (sh), 1 178m, 1 087m, 1 071111,1 008m, 988w, 94Ow, 890w, 862w, 836vw, 815w, 791w, 760w, 751w, 720vw,705wI 484 (sh), 1 460 (sh), 1 425w, 1 415w, 1 364m, 1 170m, 1 086m, 1 070m,1 OOSm, 989w, 959vw, 940w, 889w, 866vw, 839w, 816w, 789m, 762w,749w, 720w, 7OOweffectively act as chelates, while the other two contacts arisefrom the remaining substituents in symmetry-related ligands.Empirical bond valences, calculated from the relationshipS = (where R = observed Ba-0 distance, R1 =2.297, and N = 7.0), fall in the range 0.18-0.36, total 2.28; avalue of ca.2.3 is often found for barium compounds, ratherthan the ideal value of 2.0.'As in most of the alkali-metal complexes reported in the pre-vious paper, we find that for each of the ligands two of the sub-stituents lie pseudo-perpendicular to the ring plane, while theothers are more nearly parallel; in each ligand two of the latterform the chelating pair of substituents.In ligand b, however,two chelating pairs are used, as was the case in the potassiumsalt, and in both of these salts we find that in one of the chelatepairs a pseudo-normal substituent is necessarily employed.In contrast with the cyclopentadienide analogues, the anionin (4), as also in the compounds studied previously, interactswith the metal by way of the carbonyl oxygen atoms of one ormore of the carboxylate groups, and where the ratio ofpotentially co-ordinating carbonyl oxygen atoms is sufficientlyhigh relative to the number of co-ordination sites about themetal a strong tendency to chelation is observed.In thissituation, chelation tends to occur via the carbonyl oxygenatoms of a pair of COzMe substituents in which the carboxylplane is quasi-parallel to the Cs ring plane. Where the metalion is small, as is the case in the extreme example of hydrogen,the two carboxyl groups are closely coplanar with the Cs ring;in the hydrogen case the dihedral angles are (Table 6) 3.3 and0.7", and a significant related feature appears to be that the0 0 distance in this case is less than the van der Waalssum [2.431(4) A] with the hydrogen atom being almost col-linear. As the metal-atom size increases, the metal rapidlymoves out of the 0 - 0 line [0-Li-0 for example is 95.1 (3)"]and the two oxygen atoms more directly confront each other ;the tendency for the associated carboxyl groups to remaincoplanar with the Cs ring is greatly reduced.In those ligandswhich do not behave in a bis(che1ate) capacity but which aremonochelating, i.e. in the lithium and thallium salts, andligand a of the barium salt, we find dihedral angles remainingFigure. Unit-cell contents of Ba[C5(COzMe),)]z projected down C;20% thermal ellipsoids are shown of the non-hydrogen atoms. Atomlabelling within each of the Cs rings is giveJ . CHEM. SOC. DALTON TRANS. 1982 2223Table 2. Non-hydrogen atom co-ordinates for Ba[C5(COzMe)5]2Ligand a Ligand bX0.218 62(1)0.238 l(2)0.278 2(2)0.233 7(2)0.371 5(2)0.4 16 2(4)0.260 9(2)0.338 3(3)0.421 5(3)0.299 8(3)0.377 8(7)0.203 3(2)0.208 8(2)0.189 3(2)0.238 l(3)0.262 5(5)0.144 7(2)0.066 5(2)0.013 7(2)0.092 9(2)0.014 6(4)0.164 O(2)0.120 8(2)0.154 O(2)0.037 4(2)0.003 3(3)Y0.174 Ol(1)0.035 l(3)0.028 O(3)0.018 O(2)0.028 5(3)0.010 8(6)-0.010 5(3)-0.054 7(4)-0.005 l(4)-0.162 5(3)-0.211 7(6)-0.025 8(3)-0.111 2(3)-0.136 3(7)0.003 2(3)0.019 8(2)0.057 5(2)0.075 7(3)0.188 2(2)0.208 7(4)0.077 7(2)0.136 O(2)0.179 6(2)0.140 9(2)0.210 O(3)-0.004 7(2)z0.424 44( 1)0.015 7(2)0.146 7(2)0.233 7(2)0.161 7(2)0.283 4(4)-0.096 3(3)-0.104 l(3)-0.124 9(4)-0.092 6(3)-0.1 18 2(8)-0.206 3(2)-0.341 9(3)- 0.424 4(2)-0.366 3(2)-0.488 9(4)-0.162 7(2)-0.252 6(3)-0.327 4(2)-0.245 5(3)-0.322 8(5)-0.025 3(2)0.057 9(3)0.176 l(2)0.059 5(4)-0.012 8(2)X0.571 7(2)0.472 2(2)0.384 4(2)0.487 8(2)0.395 9(3)0.588 l(2)0.507 4(2)0.422 9(2)0.537 4(2)0.465 2(4)0.696 O(2)0.752 3(2)0.799 7(2)0.747 4(3)0.806 3(6)0.746 8(2)0.858 O(2)0.889 6(2)0.922 6(2)1.034 5(3)0.669 6(2)0.690 3(2)0.692 O(2)0.708 7(2)0.716 7(5)Y0.404 7(3)0.369 2(3)0.313 9(3)0.407 8(2)0.381 7(4)0.369 9(3)0.290 6(3)0.208 3(2)0.320 4(2)0.247 O(4)0.431 3(3)0.424 9(3)0.506 8(2)0.318 9(3)0.310 5(6)0.505 8(3)0.586 2(3)0.678 4(2)0.549 O(2)0.621 9(5)0.488 3(2)0.550 3(3)0.644 4(2)0.490 5(2)0.536 4(4)>z0.447 7(3)0.351 l(3)0.358 5(3)0.245 6(2)0.144 4(3)0.565 9(3)0.616 6(3)0.553 2(2)0.749 2(2)0.810 l(4)0.630 5(3)0.756 3(3)0.854 4(2)0.747 3(3)0.863 6(6)0.556 5(3)0.582 O(3)0.551 3(3)0.639 8(3)0.666 3(5)0.444 7(3)0.340 8(3)0.344 4(2)0.242 9(2)0.129 O(4)Table 3.Metal-atom environment: r is the metal-ligand distance (A); the other entries are the angles (") subtended at the metal by the ligandatoms in question. Atoms derived from ligand b are italicisedr2.707( 3)2.695(2)2.655(3)2.855(3)2.744( 3)2.932(3)2.7 6q2)2.731(2)O(51) 00 1) OW) O(31') 0(41 'I) O(51") O(41 "I)64.47(8) 78.34(8) 82.49(7) 89.44(9) 138.67(7) 150.82(7) 78.93(8)71.34(7) 126.29(8) 141.21(6) 75.81(8) 129.07(8) 73.83(7)60.88(9) 133.65(10) 100.05(10) 82.70(8) 144.05(7)73.36( 7) 1 33.24(6) 68.89(9) 141.70(9)117.24(8) 87.79( 7) 73.27(8)66.42(8) 79.61(8)127.57(8)Associated M -0-C anglesLigand a: Ba-O(11,51)-C 133.8(2), 153.1(3); Ba-O(31,4l)-C 160.0(2), 160.7(2)Ligand b: Ba-O(11,2l)-C 164.0(3), 137.5(3); Ba-O(41,5l)-C 120.8(3), 121.4(2)Transformations of the asymmetric unit: I x , y, 1 + z ; I1 1 - x , 1 - y, 1 - z ; I11 Z,y', f.below 30" with 0 * * 0 distances (w in Table 6) remaining atabout the van der Waals sum of ca.2.8 A, irrespective ofmetal-atom size. We also find the metal atom lying relativelyclose to the C5 ring plane, with the carboxyl dihedral anglespitched so that the two O(n1) atoms lie on either side of the Csplane. In the case of the bis(che1ating) ligands found in thepotassium and barium salts (ligand b) we find an ambiguoussituation brought about by the apparent impossibility of thecarboxyl substituents lying coplanar with the C5 ring.In thebarium salt (ligand b) we find one chelate to be well behavedin the above terms [0(11,21)], but the other necessarilycontains a well out-of-plane carboxyl group and is not, whilethe ligand in the potassium salt has a pair of rather poorlybehaved chelates.In the salts of H, Li, TI, and Ba (ligands a), a number ofeffects maybe observed in theligand geometries which diminishrapidly in both their effectiveness and/or precision of measure-ment as the metal size increases. C(n1)-O(n1) is longer than isthe case in the non-chelated carboxyl CO groups, irrespectiveof whether the latter act in a unidentate manner or not, andthis is particularly true of hydrogen (Table 6).C(n)-C(n1) isslightly shorter in chelated carboxyl groups, and C(n)-C(n'),i.e. the ring bond in the chelate, is very appreciably lengthened.Angular geometry appears to not be greatly affected; how-ever, the 0-C-0 angle is diminished in the derivatives of Hand Li relative to the remainder.Within the C5 ring, the C-C distances not involved in chelaterings lie around 1.40 A; this is shorter than in [Ru{q-C5-(COzMe)5}(q-C5H5)] (ca. 1.44 A).' The latter value is in goodagreement with the general run of C-C distances in [M(q5-C5Hs)2] complexes, while the value of 1.40 8, compares moreclosely with the value of 1.38(1) A found in [Na(C5H5)-(Me2NCH2CH2NMe2)], to which is ascribed an ionic structurein spite of an q5 confrontation with the sodium afom.lo In allderivatives, C(n1) exhibit varying deviations from the C5plane, >0.1 8, being not unusual; these deviations do notcorrelate with carboxylate dihedral angles or mode of co-ordination2224 J.CHEM. SOC. DALTON TRANS. 1982Table 4. Ligand non-hydrogen geometries: distances (A), angles (")LigandF ,a1.395(5)1.407(5)1.395(5)1.407(4)1.435(5)1.461(4)1.462(7)1.461(4)1.482(5)1.449(5)1.222(4)1.195(6)1.207(5)107.7(3)108.4(4)108.2( 3)108,8( 3)106.9(3)1 28.7( 3)1 23 4 4 )128.3(3)123.0(3)126.6(4)1 25.1 (3)123.4(2)127.4(3)125.8( 3)127.2(2)126.8(3)126.6(5)125.564)b1.437(4)1.400(4)1.416(4)1.404(4)1.398(4)1.460(4)1.470(4)1.487(5)1.457(4)1.492(4)1.203(4)1.214(3)1.204(4)107.3(2)107.6(3)108.4(3)1 0 7.6(2)109.0(3)124.4(3)128.1(3)1 27.2(3)125.1(3)128.0(3)12333)129.4(3)122.9(3)124.7(3)126.2(3)128.0(3)127.4(3)124.3(4)C(4 I) -0(4 1 )C( 5 1) -0( 5 1)C(11)-O(12)C(21) -0(22)C(31)-O(32)C(41)-O(42)C( 5 1 ) -0( 52)O( 12)-C( 12)0(22)-C(22)0(32)-C(32)O(42) -C(42)o(52) -C( 52)C(4)-C(41) -0(41)C(5) -C(5 1) - 0 ( 5 1)C( 1) -C( 1 1) -O( 1 2)C(2) -C(21) -O(22)C(3) -C(3 1) -0( 32)C(4) -C(41) -0(42)C( 5 ) €( 5 1) -0(52)O( 1 1)-C( 1 1 )-o( 12)0(21)-C(21)-0(22)Of3 1)€(3 1) -O( 32)0(41)-C(41)-0(42)O(5 1) -C(5 1)-O(52)C(11) -0(12)-C(12)C(21) -O( 22) -C(22)C(31)-0(32)-C(32)C(41) -0(42) -C(42)C(5 1) -0( 52) -C(52)Ligandr Aa1 .206(3)1.210(3)1.33 l(5)1.312(6)1.338(7)1.327(4)1.343(4)1.456(6)1.548(11)1.437(7)1.431(7)1.445(6)123.0(3)1 26.8( 3)11 1.6(3)109.3(4)1 12.0(3)114.3(2)11 1.6(2)121 3 3 )124.0(6)122.6(3)122.7(3)12 1.5( 3)117.3(3)107.7(4)118.0(5)115.3(3)11 5.6(2)b1.221(4)1.202(5)1.3 3 7(4)1.346(4)1.328(6)1.332(5)1.321(4)1.437(5)1.441(5)1.435(8)1.445(5)I .457(6)123.3(3)125.0(3)11 1 3 3 )1 11.2(2)112.3(2)11 3.9(3)112.2(3)1 20.6( 3)121.3(3)123.3(4)122.7(3)1 22.8(3)117.1(3)1 16.2(2)114.4(3)117.8(4)116.2(4)Table 5.Ligand least-squares planes given in the form pX + q Y +rZ = s, where the right-hand orthogonal 8, frame (X,Y,Z) isdefined with Xparallel to a and 2 in the ac plane.o (defining atoms)and atom deviations 6 are given in A. Defining atoms are C(1)-C(5). e(n)/" is the dihedral angle to the plane defined by C(n,nl)-O(n1,2)Ligand --- a b4 1948 9881.7050.0030.003-0.001-0.0020.003-0.004-0.0930.1160.080-0.1270.044- 0.6331.0820.519-1 280-6 0307 3483 1061.2250.006-0.0050.008-0.0070.0040.0010.0660.106- 0.01 1-0.0140.0100.286 - 0.2970.86660(41)60(51)60( 12)60(22)60(32)60(42)6C( 12)6C(22)6C(32)6C(42)6C(52) e we(2)e(3)e(4)e(5)Ligande - 7 a b-1.1280.3580.447- 1.045-0.405-0.271-0.928- 0.205-0.0950.9600.3100.82127.174.124.569.916.40.5410.9980.740-0.131-1.119-0.714-1.209-0.0480.873- 1.209-0.812- 1.30010.528.763.334.288.0ExperimentalGeneral experimental conditions have been described pre-viously .lPreparation of M[C5(C02Me),]2.-(a) From the metalacetate.Magnesium ac6tate (122 mg, 0.85 mmol) was addedto a solution of HC5(C02Me)5 (500 mg, 1.4 mmol) in methanol(10 cm3). After 2 h, the filtered reaction mixture was evapor-ated to dryness. Recrystallisation (MeOH) of the residueafforded white Mg[C5(C02Me)5]2*H20 (1) (191 mg, 5379,m.p. >300 "C (Found: C, 48.1; H, 3.90. C30H32Mg021requires C, 47.85; H, 4.25%).(6) From the metal carbonate. Calcium carbonate (74 mg,0.74 mmol) was added to an aqueous solution of HC5(C02Me)5(500 mg, 1.4 mmol).Rapid evolution of C02 occurred, afterwhich the solution was filtered. The filtrate was then reducedin volume until crystals formed on cooling. These were collec-ted and recrystallised (MeOH) to give white Ca[C5(C02Me)5]2(2) (322 mg, 58%), m.p. 295-298 "C (Found: C, 47.9; H, 3.90.C30H30Ca020 requires C, 48.0; H, 4.00%). Conductivity (H20) :A 130 ohm-' cm2 mol-'.The following compounds were similarly prepared :white Ba[C5(C02Me)5]2 (4) (78%), m.p. >300 "C (Found:C, 42.45; H, 3.50. C30H30Ba020 requires C, 42.5; H, 3.55%);this compound was dried by azeotropic distillation of waterwith a benzene-ethanol mixture ; white Zn[C5(C02Me)5]2'3H20 ( 5 ) (57%), m.p. 185 "C (decomp.) (Found: C, 43.55; H,4.10.C30H36023Zn requires C, 43.4; H, 4.35%); co-ordinatedwater was not removed after heating for 8 h at 100 "C in vacuo ;white Cd[Cs(C02Me)5]2 (6) (44%), m.p. >300 "C (Found: C,43.75; H, 3.55. C30H30Cd020 requires C, 43.75; H, 3.65%).(c) From flte metal chloride. A solution of Tl[C5(C02Me)5](281 mg, 0.5 mmol) in methanol (15 cm3) was added to asolution of SrC12*6H20 (69 mg, 0.26 mmol) in methanol (1J. CHEM. SOC. DALTON TRANS. 1982 2225Table 6. ' Ionic ' ligand parameters: a tabulation of a number of significant ligand parameters for the compounds of ref. 1 and the presentcomplex about the vicinity of the pairs of chelating ligand substituents CO-OMe at ring carbon atoms I , m where I < m. Also given are rangesO hIuOMeR, for the same parameters about the non-chelating ligand substituents (square brackets denote a single valu-i: only).Angles x are the dihedralangles between the carboxyl plane defined by C-CO,(l) and the ring plane and 6 is the deviation of the metal atom from the carboxylplane and A the deviation from the ring plane. All distances are in A and all angles in degrees. In each entry the upper value correspondsto the first of the two oxygen atoms and the lower to the second. In relevant cases, parameters of the qS-CS(C02Me)s group in [Ru(Cs-(C02Me)s>(CsHs)] are included for comparisonCompound/ HligandChelate O(4 1 )system O(51)DistanceslAY 1.12(7)1.32(7)s 1.256(3)1.259(4)1.205(4)t 1.428( 5 )1.426(4)1.498(5)u 1.316(4)1.320( 5 )1.342(4)u 1.453(5)R, 1.396(3)-1.410(5)w 2.431(4)6 0.150.07RsA 0.07R, 1.194(4)-R, 1.460(3)-R, 1.328(4)-171(3)1 09.8( 1 6)109.8( 13)1 25.2( 7)12533)12533)116.1(2)115.4(3)1 12.0(3)118.7(3)119.1(3)125.0(3)127.6(2)126.9(3)128.4(3)107.3(2)1 07.2(2)108.8( 3)125.1(3)126.0(3)3.30.78.8124.q3)-1 09.5(2)-123.1(2)-122.9(2)-108.1(2)--88.1Li K1.914(7) 2.657(3)1.900(7) 2.862(3)1.2 1 O(5)1.212(5)1.198(5)1.453(5)1.450(5)1.191(6)-1.461(6)-1.499( 5 )1.338(4)1.345(4)1.323(5)-1.334(5)1.447(5)1.393(5)-1.41 5(5)2.813(3)0.8070.780[0.675]0.54095.1 (3)1 38.1(3)1 38.3( 3)127.2(3)128.1(3)126.0(4)112.2(3)11 1.7(3)110.3(4)-1 12.0(3)1 20.5( 3)120.3(3)123.7(4)128.2(3)1 28.5( 3)128.3(3)107.2(3)107.3(3)109.2(3)1 24.5(3)1 23.9( 3)4.424.05.6-90.0125..'3(4)-122.6(4)-123.3(3)-107.7(3)-1.199(5)1.229(5)1.203(5)1.478(5)1.446(5)1.457(6)1.335(5)1.331(5)1.340(5)1.4 16(6)1.404(5)-1.426(5)3.039( 4)1.8942.092[ 1.92610.99566.7( 1)134.6(3)132.1(3)125.7(4)126.2(4)[126.6(4)1110.5(3)1 12.0(3)[111.5(3)]1 23.8(4)121.8(4)[ 12 I .9(4)]126.7(3)126.3(3)126.2(4)108.2( 3)10733)[107.9(3)]125.8(4)-125.2(4)126.2(4)56.020.5[35.7]KO(3 1)O(4 1)2.762(3)2.726( 3)1.208(5)1.217(5)[ 1.203(5)]1.484(6)1.464( 5 )[ 1.457(6)]1 .329( 5 )1.338(5)[1.340(5)11.394(5)1.404(5)-1.426(5)3.041(4)2.2981.906[ 1.92610.49367.3( 1)123.1(3)136.7(3)125.9(4)125.4(4)[ 1 26.6( 4)]110.7(3)112.1(3)[I 11.5(3)]123.4(4)122.5(4)[ 121.9(4)]125.3(3)124.0(3)126.2(4)108.7( 3)107.8( 3)[ 107.9(3)]126.0(4)127.8(4)125.8(4)-62.534.1[35.7]TIO(21)O(3 1)2.822( 5 )2.682( 5 )1.204(7)1.207(7)1.212(8)1.474(8)1.451(7)1.458(8)-1.487(8)1.334(7)1.343(7)1.327(7)-1 .340( 5 )1.448(7)1.4247)2.820( 7)1.1971.8160.5341 .I 79( 8)-1.386(8)-61.6( 1)148.2(4)137.3(4)1 27.9( 5)1 25.6( 5 )125.0(5)109.1(4)113.2(5)11 135)-112.6(5)123.0(5)121.2(5)123.q5)-1 24.1(5)128.1(5)125.4(5)128.1(5)107.6(5)107.3(4)109.0(5)1 24.2( 5 )127.3(5)27.425.910.8-77.7123.3(5)-123.6( 5)-107.8(5)-Ba/a Ba/b2.707(3)2.695(2)1.222(4)1.210(3)1.207( 5 )1.461(4)1.449(5)1.482(5)1.331(5)1.343(4)1.3 12(6)-1.338(7)1.435(5)1.395(6)-1.407(4)2.881(4)1.8580.9201.195(6)-1.461(4)-2.655(3)2.855(3)1.203(4)1.214(3)[1.204(4)11.460(4)I .470(4)[ 1.487(5)]1.337(4)1.346(4)[1.328(6)]1.437(4)1.398(4)-1.41 6(4)2.796(4)0.2071.9090.173 0.56164.47(8)1 3 3.8(2)1 53.1 (3)1 26.8( 3)126.8(3)126.6(5)1 11.6(3)11 1.6(2)1 09.3( 4)121.5(3)121.5( 3)122.6(3)-124.0(6)1 28.7( 3)127.2(2)128.3(3)1 07.7( 2)106.9( 3)1 08.8( 3)123.4(4)1 25.8( 3)27. I16.424.5123.q3)-- 114.3(2)123.0(3)-108.2(3)--74.160.88(9)164.0(3)13733)128.0(3)127.4(3)[ 124.3(4)]111.5(3)1 11.2(2)[112.3(2)]120.6( 3)121.3(3)[ 1 23.3(4)]128.1(3)1 27.2( 3)128.0(3)1 07.3(2)1 07.6( 3)[ 108.4( 3)]124.4(3)125.1(3)1 2 3 3 3)-10.528.7[63.3]Ba/bo(41)O(51)2.932(3)2.760(2)1.221(4)1.202( 5 )1.204(4)]I .457(4)1.492(4)1.487(5)]1.3 32( 5 )1.321(4)1.328(6)]1.404(4)1.398(4)-1.4 1 6(4)3.120(4)1.5201.5373.14166.42( 8)120.8(3)12142)123.3(3)125.0(3)[ 124.3(4)1113.9(3)112.2(3)[112.3(2)]122.7(3)122.8(3)[ I23.3(4)]122.9(3)124.7(3)128.0(3)1 07.6(2)109.0( 3)[ 108.4( 3)]123.5(3)-1 29.4( 3)126.2(3)34.288 .O[63.3]Ru1.192(2)-I .200(2)1.485(2)-1 .502(2)1.331(2)-1.335(3)1.430(2)-1.442(2)I .796121.3(2)-125.9(2)108.8(1)- 113.7(1)124.8(2)-125.3(2)122.4( 1)-128.7(1)107.8(1)-1 O8.4f 1 )5.2- 89.2226 J .CHEM. SOC. DALTON TRANS. 1982cm3). Immediate precipitation of TIC1 occurred, and after 2 hthe mixture was filtered. Evaporation and recrystallisation(MeOH) afforded white Sr[Cs(C02Me)s]2*3H20 (3) (51%),m.p. 218 "C (decomp.) (Found: C, 42.45; H, 4.20. C30H36'023Sr requires C, 42.3; H, 4.25%). Conductivity (H20): A155.6 ohm-' cm2 mol-'.Crystalloguaphy.-The general procedure was outlined inthe previous paper.'Crysral data. C30H30Ba020, M = 847.9, Triclinic, spacegroup Pf (C:, no. 2), a = 14.499(4), b = 12.940(4), c =U = 1736.1(7) A3, D, = 1.62(1), 2 = 2, D, = 1.62 g ~ m - ~ ,F(000) = 852, specimen size 0.24 x 0.12 x 0.06 mm (platemounted in capillary), pMo = 11.8 cm-', N = 10 549, No =8 173, R,R', S = 0.036, 0.047, 1.43.Data acquisition was terminated at h = 14 due to instru-ment malfunction, in consequence the intensities of a smallnumber of very strong reflections were not determined andthese are omitted from the structure-factor listing.10.745(2) A, cc = 100.54(2), B = 100.02(2), y = 114.23(2)",ConclusionsThe Group 2A metals all form hydrocarbon analogues of thecompounds reported above, which are unstable in air, andrapidly hydrolyse in contact with In the vapourphase,I4 both Mg(CsH& and Ca(C5H& have structures inwhich the C5 rings are symmetrically attached to the metal ion.In the crystal, the structure of the magnesium compound isthe same,15 but the calcium derivative adopts a polymericstructure in which each calcium is co-ordinated by one 0,one q3, and two qs rings.16 In both cases, the interaction isdescribed as ionic (' electrostatic '), i.e.the compounds areM2+(CsH5-)2. The zinc analogue has covalent ring-metalbonds, but is also air- and water-sensitive.l' No cadmiumderivative has been reported. The pmcp compounds describedabove all showed the marked stability now expected of deriv-atives containing the new ligand. On the basis of their i.r.spectra, and the X-ray structure determination, all are con-sidered to have the pmcp group attached via metal-oxygenbonds; in the zinc case, and perhaps also the magnesium andstrontium compounds, one or more co-ordination sites areprobably occupied by water molecules.AcknowledgementsWe thank the Australian Research Grants Committee forsupport of this work and Mr.M. L. Williams for the i.r.spectra.ReferencesM. 1. Bruce, J . K. Walton, M. L. Williams, S. R. Hall, B. W.Skelton, and A. H. White, preceding paper.B. Metz, D. Moras, and R. Weiss, Acta Crystallogr., Sect. B,1973, 29, 1388; D. L. Hughes, C. L. Mortimer, and M. R.Truter, ibid., 1978, 34, 800; Znorg. Chim. Acta, 1978, 29, 43;J. Feneau-Dupont, E. Arte, J. P. Declerq, G. Germain, and M.van Meerssche, Acta Crystallogr., Sect. B, 1979, 35, 1217.T. Watanabe and M. Matsui, Acta Crystallogr., Sect. B, 1978,34,273 1.J-C. Mutin, A. Courtois, G. Bertrand, J. Protas, and G. Watelle-Marion, C.R. Acad. Sci., Ser. C , 1971, 273, 1512.Y. Dusausoy, J. Protas, J-C. Mutin, and G. Watelle, ActaCrystallogr., Sect. B, 1970, 26, 1567.6 J. C. Voegel, J. C. Thierry, and R. Weiss, Acta Crystallogr.,Sect. B, 1974, 30, 70.7 B. Metz, D. Moras, and R. Weiss, Acta Crystallogr., Sect. B,1973,29, 1382.8 I. D. Brown and K. K. Wu, Acta Crystallogr., Sect. B, 1976, 32,1957.9 M. I. Bruce, B. W. Skelton, R. C. Wallis, J. K. Walton, A. H.White, and M. L. Williams, J. Chem. SOC., Chem. Commun.,1981,428.10 T. Aoyagi, H. M. M. Shearer, K. Wade, and G. Whitehead, J.Chem. Soc., Chem. Commun., 1976, 164.1 1 G. Wilkinson, F. A. Cotton, and J. M. Birmingham, J. Inorg.Nucl. Chem., 1956, 2, 95.12 E. 0. Fischer and A. Treiber, Chem. Ber., 1961, 94, 2193.13 R. Zerger and G. Stucky, J. Organomet. Chem., 1974,80, 7.14 A. Haaland, J. Lusztyk, D. P. Novak, J. Brunvoll, and K. B.Starowieyski, J. Chem. SOC., Chem. Commun., 1974,54.15 W. Bunder and E. Weiss, J. Organornet. Chem., 1975, 92, 1.16 R. Zerger and G. Stucky, J. Organomet. Chem., 1974,80, 7.17 E. 0. Fischer, H. P. Hofmann, and A. Treiber, Z. Nuturforsch.,Teil B, 1959, 14, 599.Received 3rd March 1982; Paper 2/38
ISSN:1477-9226
DOI:10.1039/DT9820002221
出版商:RSC
年代:1982
数据来源: RSC