Coordination of Polythiaether Macrocycles to Metal Cluster

Apr 1, 1995 - Gregory E. D. Mullen, Philip J. Blower, Daniel J. Price, Anne K. Powell, ... Andrew J. P. White, David J. Williams, and James D. E. T. W...
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1739

Organometallics 19995, 14, 1739- 1747

Coordination of Polythiaether Macrocycles to Metal Cluster Complexes. 2. Coordination of Polythiaether Macrocycles to Hexaruthenium Carbido Carbonyl Clusters Richard D. Adams," Stephen B. Falloon, Kenneth T. McBride, and John H. Yamamoto Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208 Received November 28, 1994@

The synthesis and structural characterizations of Rus(p6-C) cluster complexes containing the polythiaether macrocycle ligands 1,5,9-trithiacyclododecane(12S3), 1,5,9,13-tetrathiacyclohexadecane (16S4), and 1,4,74rithiacyclononane (9S3) are reported. The reactions of Rus(CO)1&@2), 1, with 12S3 and 16S4 in refluxing octane solvent have yielded the new 2, in 78% yield, and Rus(C0)1jCu-);12-16S4)016cluster complexes R~~(C0)1301-11~-12S3)016-C), C), 3,in 58%yield, respectively. The reaction of 1with 9S3 in refluxing hexane solvent has 4, in 93% yield. All three products yielded the new cluster complex Rus(co)14(r3-9s3)~6-c), were characterized by a combination of IR, 'H NMR, and single crystal X-ray diffraction analyses. All three compounds contain octahedral RUGclusters with a carbido ligand in the center. In compound 2 the three sulfur atoms of the 12S3 ligand are coordinated to one ruthenium atom but one of the sulfur atoms simultaneously serves as a bridge to an adjacent ruthenium atom. In compound 3 only two of the four sulfur atoms of the 16S4 ligand are coordinated to the cluster and they are coordinated to two adjacent ruthenium atoms. In compound 4 the three sulfur atoms of the 9S3 ligand are coordinated to one ruthenium atom only. When heated t o 105 "C for 18 h, compound 4 was converted to the new compound Ru6(CO)&3-q3-SCH2CH2SCH2CH2S)(p5-C), 5, in 68% yield. The evolution of ethylene was observed by lH NMR spectroscopy. Compound 5 was obtained in one step from the reaction of 1 with 9S3 in refluxing octane solvent in 36% yield. Compound 5 was characterized crystallographically and was shown to consist of a "spiked" square pyramidal cluster of six metal atoms with the carbido ligand in the center of the base of the square pyramid. The spike is bonded to one of the metal atoms in the base of the square pyramid. The 9S3 ligand was converted into a triply bridging 3-thiapentane-1,5-dithiolato ligand. All three sulfur atoms form bridges between the ruthenium spike and the Rug square pyramid. Crystal data: for 2*C6H6,space group = Pi, a = 16.755(2) b = 11.647(2) c = 11.355(2) A, a = 61.30(1)", ,8 = 89.78(1)", y = 101.76(2)", 2 = 2 2648 reflections, R = 0.032; for 3: space group = P n m a , a = 23.373(3) A, b = 17.643(2) c = 9.453(2) Z = 4, 1854 reflections, R = 0.030; for 4*C,&, space group = P21/a, a = 13.366(2) b = 20.746(6) c = 13.059(3) ,8 = 90.75(1)", 2 = 4, 3345 reflections, R = 0.025; for SCH2C12, space group = P21/c, a = 13.669(2) b = 15.610(3) c = 15.476(2) ,B = 92.46(1)", 2 = 4, 4526 reflections, R = 0.033.

A,

A,

A,

A,

A,

We have recently developed new procedures for the preparation of polythiaether macrocycles that involve the catalytic cyclooligomerization of thietanes, eq (1).1,2 Polythiaether macrocycles have recently attracted attention because of their ability to serve as ligands for the transition element^.^ To date, however, there have been very few reports on metal carbonyl cluster com-

0276-7333/95/2314-1739$09.00/0

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A,

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Introduction

@Abstractpublished in Advance ACS Abstracts, March 15, 1995. (1)( a ) Adams, R. D.; Falloon, S. B. J . Am. Chem. SOC.1994,116, 10540.(b)Adams, R.D.; Cortopassi, J . E.; Falloon, S. B. J . Organomet. Chem. 1993,463, C5. (2) Adams, R. D.; Falloon, S. B. Organometallics 1995,14, 1748. ( 3 ) ( a ) Cooper, S. R., Ed. Crown Compounds: Toward Future Applications; VCH Publishers: New York, 1992. (b)Cooper, S. R.; Rawle, S. C. Struct. Bonding 1990,72,l.(c) Blake, A.J.; Schroder, M. Adu. Inorg. Chem. 1990,35,1. (d) Cooper, S.R. Acc. Chem. Res. 1988, 21, 141.

A,

n

HZC-CH,

l

l

5-CH,

-

R e ) cluster catalyst

ihietrnr

1253, 17-3

U 1654, n r 4

U 2456, 17-6

plexes that contain polythiaether macrocycles as ligand~.~.j We have recently shown that the trithia macrocycle 12S3 can be attached to the pentaruthenium carbido carbonyl cluster complex Ruj(C0)1j(uj-C)in a

0 1995 American Chemical Society

1740 Organometallics, Vol. 14,No. 4, 1995

Adams et al.

slow purge with nitrogen. After cooling of the solution to room temperature, a brown precipitate formed. The solid was washed with 3 x 10 mL portions of hexane and then dissolved with 30 mL of CH2C12, and the mixture was filtered under nitrogen. The solvent was then removed under vacuum to yield 6.8-mg of RU6(co)15(p-)72-16s4)(~~6-c), 3, in 58% yield. Analytical samples were obtained by recrystallization by slow evaporation of solvent from a CHzClAexane (2/1)solution at -20 "C. Spectral data for 3 are as follows. IR (VCO,cm-l, CHzCl2): 2073 (m),2033 (s), 2018 (vs),2003 (m, sh), 1969 (w), 1825 (w). lH NMR (6 in CDC13): 2.47-2.77 (m, 8H), 3.34-3.48 (m, 16H). Anal. Calc (found) for 3: C, 25.19 (25.45);H, 1.81 (1.81). Preparation of Rus(C0)14(rl3-9S3)Ols-C), 4. A 20.0-mg amount of 1 (0.0183 mmol) and 3.9 mg of 9S3 (0.022 mmol) 1684 9s3 12S3 were dissolved in 30 mL of hexane, and then the solution was heated to reflux with a nitrogen purge for 4 h. The solvent was then removed under vacuum, and the crude product thiacyclohexadecane (16S4),and 1,4,7-trithiacyclononane dissolved in a minimal amount of CHzClz and separated by (9S3) to the hexaruthenium carbido cluster Rug(co)17column chromatography on silica gel (12 mm x 200 mm). (ps-c),1, are described. These studies further demonElution with hexane yielded 4.4 mg of unreacted RU6(C0)1&6strate that the thiaether ligands are able to change their C), and elution with CHzClz yielded 15.9 mg of RUs(C0)14()7~conformations in order to serve as more effective 9S3)(p&), 4, in 93% yield (based on 1 consumed). Analytical ligands. We have also found additional evidence that and spectral data for 4 are as follows. IR (VCO,cm-l, in CHZthose ligands that contain CzH4 groupings between pairs Clz): 2066 (m), 2017 (vs), 1975 (w, br), 1800 (w, br). 'H NMR of sulfur atoms are subject to degradation through the (6 in CD2C12): 2.78 (m, 6H, 2 J ~ = -13.9 - ~ Hz, 3 J ~=- 7.0 ~ elimination of CzH4 under mild conditions. The 9S3 HZ, 3 J ~=-6.7 ~ HZ), 2.33 (m, 6H, 2 J ~=--13.9 ~ HZ, 3 J ~=- ~ complex R~s(C0)14(17~-9S3)CUs-C), 4, was found to un7.0 Hz, 3 J ~=- 6.7 ~ Hz). Anal. Calc (found) for 4 (crystals obtained from CH2C12): C, 21.18 (20.38); H, 1.02 (1.05). dergo elimination of ethylene to yield a new hexanuclear Preparation of Rus(C0)14~s-;r13-SCH~CH~SCH2CH~S)complex Ru~(CO)~~~~-~~-SCHZCHZSCHZCHZS)~~-C), 6, @&), 5. A 20.0-mg amount of 1 (0.0183 mmol) and 3.9 mg containing a 3-thiapentane-l,5-dithiolato ligand when of 9S3 (0.022 mmol) were dissolved in 30 mL of octane, and heated to 105 "C. then the solution was heated t o reflux with a nitrogen purge for 2 h. The solvent was then removed under vacuum, and Experimental Section the crude product was dissolved in a minimal amount of CHzCl2 and separated by column chromatography on silica gel (12 General Data. Reagent grade solvents were stored over mm x 200 mm). Elution with hexane yielded 1.2 mg of 4i% molecular sieves. All reactions were performed under a unreacted Ru6(C0)17(p&), and elution with CHzCl:, yielded nitrogen atmosphere. Infrared spectra were recorded on a Cin H 36% ~CH~S)~~-C) 7.3 mg of R U ~ ( C ~ ) ~ ~ C U ~ - ) ~ ~ - S C H ~ C H ~ S5, Nicolet 5DXB FTIR spectrophotometer. lH NMR spectra were yield. Analytical and spectral data for 5 are as follows. IR recorded on a Bruker AM-500 FT-NMR spectrometer. Ru6(VCO,cm-l, in CH2C12): 2085 (s), 2056 (vs),2035 (m), 2022 (vs), (cO)17(pf,-c), 1, was prepared by the previously reported 2003 (m, sh), 1975 (w, br). 'H NMR (6 in CD2Clz): 4.26 (dd, procedure.6 1,5,9-Trithiacyclododecane,12S3, was prepared J =7.5 Hz, 13.0 Hz, lH), 3.91 (dd, JH-H= 7.9 Hz, JH-H = 13.3 by the catalytic cyclooligomerization of thietane.'" 1,5,9,13Hz, lH), 3.65 (dd, JH-H= 5.5 Hz, 10.6 Hz, lH), 3.3-3.42 (m, Tetrathiacyclohexadecane,16S4, and 1,4,7-trithiacyclononane, = 11.0 Hz, 11.0 Hz, lH), 2H), 3.2 (ddd, JH-H= 7.9 Hz, JH-H 9S3, were purchased from Aldrich Chemical Co. and were used 2.9 (ddd, JH-H = 8.3 Hz, 11.0 Hz, 11.0 Hz, lH), 2.5 (ddd, JH-H without further purification. Elemental analyses were per= 6.6 Hz, 10.8 Hz, 13.2 Hz, 1H). Anal. Calc (found) for 5CHzformed by Oneida Research Services, Whitesboro, NY. Clz: C, 19.25 (20.23); H, 0.81 (0.42). Preparation of R~~(C0)13~-t1~-12S3)(Cle-C), 2. A 20.0Conversion of 4 to 5. An NMR tube was charged with a mg amount of 1 (0.0183 mmol) and a 5.3-mg amount of 12S3 4.5 mg sample of 4 in toluene-& under a nitrogen atmosphere (0.024 mmol) were dissolved in 30 mL of octane. The solution and placed in an oil bath at 105 "C for 18 h. An NMR spectrum was brought to reflux and maintained for 4 h in the presence recorded after this period showed the formation of ethylene of a slow purge with nitrogen. After cooling of the solution to as a sharp singlet at 5.25 ppm. The solvent was then removed, room temperature, a brown precipitate formed. The solid was and 3.0 mg of 5 (68% yield) was isolated from the sample by washed with 3 x 10 mL portions of hexanes and dissolved with TLC. 30 mL of CHzClZ, and the mixture was filtered under nitrogen. The solvent was removed under vacuum. This yielded 17.2Reaction of R~s(CO)ls01-t1~-12S3)(lrs.C), 2, with CO. A 25.0-mg amount of 2 was dissolved in 40 mL of THF, and the mg of RUs(C0)13(p-)73-12S3)(p6-C), 2, in 78% yield. Analytical samples were obtained by recrystallization from CHzCld solution was heated to reflux under a slow purge of CO for 5 benzene (2/1) solutions by slow evaporation of solvent at 25 h. The solvent was then removed under vacuum and the crude "C. Analytical and spectral data for 2 are as follows. IR (VCO, product separated by TLC using a CH2Clfiexane (1:l)eluant. cm-', in CH2ClZ): 2078 (m), 2039 (vs), 2024 (vs), 1999 (m, sh), This yielded 10.0 mg of 1 (45% yield). 1975 (w, sh), 1836 (w). 'H NMR (6 in CDC13): 3.1 (m, 4H), Crystallographic Analysis. Crystals of 2 suitable for 2.85 (dd, 4H), 2.57 (dd, 4H), 2.2 (m, 4H), 1.84 (q, 2H). Anal. diffraction analysis were grown by slow evaporation of solvent Calc (found)for 2CsH6: C, 27.15 (26.38); H, 1.88 (1.72). from a solution in a CHzClhenzene (2/1) solvent mixture at Preparation of R~s(CO)~s~-1~-16S4)(ue.C), 3. A 20.025 "C. Crystals of 3 and 5 suitable for diffraction analysis were mg amount of 1 (0.0183 mmol) and 6.5 mg of 16S4 (0.022 grown by slow evaporation of solvent from a solution in a CHzmmol) were dissolved in 30 mL of octane. The solution was Clhexane (2/1) solvent mixture at -20 "C. Crystals of 4 brought to reflux and maintained for 2 h in the presence of a suitable for diffraction analysis were grown by slow evaporation of solvent from a solution in a CH~Clz/benzene(211)solvent (4)Edwards, A. J.;Johnson, B. F. G . ;Khan, F. K.; Lewis, J.;Raithby, mixture at 25 "C. All crystals used for the diffraction P.R. J. Organomet. Chem. 1992, 426, C44. measurements were mounted in thin-walled glass capillaries. (5)Adams, R. D.; Falloon, S. B.; McBride, K. T. Organometallics Diffraction measurements were made on a Rigaku AFCGS fully 1994, 13, 4870. automated four-circle diffractometer using graphite-monochro(6)Nicholls, J. N.; Vargas, M. D.Inorg. Synth. 1983,26, 281 sequence of decarbonylation steps that leads ultimately to a tridentate coordination in which one of the sulfur atoms also serves as a bridge between two metal atomsS5 In this report, the results of our studies of the complexation of three different polythiaether macrocycles 1,5,9-trithiacyclododecane(12S3), 1,5,9,13-tetra-

Organometallics, Vol. 14,No.4, 1995 1741

Hexaruthenium Carbido Carbonyl Clusters

Table 1. Crystallographic Data for Compounds 2-5 compound

2 empirical formula fw cryst system lattice garams a (A) h c (A) a (deg)

(4)

space group 2 value D,,I, (g/cm') p(Mo Ka)(cm-I) temp ("C) 2&,, (deg) no. obs I > 3u(O no. variables residuals:" R; R,

GOF max shift final cycle largest peak in final diff map (e/A3) abs corr, madmin

3

4

RU6s301xC2xH1nChHh 1283.10 triclinic

R U ~ S ~ O I S C ? X H ? ~ R w S ~ O I KI ?HilCbHh 1335.15 1269.03 orthorhombic monoclinic

16.755(2) I1.647(2) 11.355(2) 6 1.30(1) 89.78(I ) 101.76(2) 18_89.5(6) P 1 (No. 2)

23.373(3) I 7.643(2) 9.453(2) 90.0 90.0 90.0 3898.2(8) Pnma (No. 62) 4 2.28 25.45 20 46 1854 256 0.030; 0.030 1.49 0.04 0.43 empirical, 1.0/0.79

L

2.26 25.63 20 41 2648 430 0.032;0.028 1.56 0.01 0.85 empirical, I .0/0.83

mated Mo K a radiation. The unit cells of the crystals were determined and refined from 15 randomly selected reflections obtained by using the AFC6 automatic search, center, index, and least-squares routines. Crystal data, data collection parameters, and results of the analyses are listed in Table 1. All data processing was performed on a Digital Equipment Corp. VAXstation 3520 computer by using the TEXSAN motif structure solving program library obtained from the Molecular Structure Corp., The Woodlands, TX. Neutral atom scattering factors were calculated by the standard procedure^.^^ Anomalous dispersion corrections were applied to all non-hydrogen atoms.7b Lorentz/polarization ( L p )and absorption corrections (empirical based on v-scans) were applied to the data for each structure. Full matrix least-squares refinements minimized the function E:hklw(lFol - lFc1)2,where w = l/a2(F),d F ) = u(Fo2)/2FO, and a(Fo2)= [ d I r a w ) ' + (0.02Znet)211'2/Lp. Compound 2 crystallized in the triclinic crystal system. The space group P i was assumed and confirmed by the successful solution and refinement of the structure. The structure was solved by a combination of direct methods (MITHRIL) and difference Fourier syntheses. All non-hydrogen atoms were refined with anisotropic thermal parameters. The positions of the hydrogen atoms on the 12S3 ligand were calculated by assuming idealized tetrahedral geometries at the carbon atoms with C-H distances of 0.95 A. The scattering contributions of the hydrogen atoms were included in the structure factor calculations, but their positions were not refined. In the final stages of the analysis two formula equivalents of benzene that had cocrystallized from the crystallization solvent were located in the lattice. There were both centered about centers of symmetry. They were added to the analysis and satisfactorily refined with isotropic thermal parameters for the carbon atoms. Compound 3 crystallized in the orthorhombic crystal system. The patterns of systematic absences observed during the collection of the intensity data were consistent with either of the space groups Pnma or Pna21. The centrosymmetric space group Pnma was selected and confirmed by the successful solution and refinement of the structure. The structure was solved by a combination of direct methods (MITHRIL) and (7) (a) International Tables for X-ray Crystallography; Kynoch Press: Birmingham, England, 1975; Vol. IV, Table 2.2B, pp 99-101. (b) Ibid., Table 2.3.1, pp 149-150.

S

R u ~ S I~4COI YHI ~ C H ~ C I ? 1247.80 monoclinic

13.366(2) 20.746(6) 13.059(3) 90.0 90.75( 1) 90.0 362 1( 1) P21/a(No. 14) 4 2.33 26.23 20 44 3345 452 0.025; 0.025 I .41 0.02 0.48 empirical, 1.0/0.66

063

13.669(2) 15.6lO(3) 15.476(2) 90.0 92.46( I ) 90.0 3299.1(8) P21/c (NO. 14) 4 2.5 1 30.90 20 48 4526 402 0.033; 0.042 2.52 0.15 1.24 empirical, 1.0/0.66

061

Figure 1. ORTEP diagram of RUs(C0)1301-r3-12S3)OLs-C), 2, showing 40% probability thermal ellipsoids. difference Fourier syntheses. All non-hydrogen atoms were refined with anisotropic thermal parameters. The positions of the hydrogen atoms on the 16S4 ligand were calculated by assuming idealized tetrahedral geometries at the carbon atoms with C-H distances of 0.95 A. The scattering contributions of the hydrogen atoms were included in the structure factor calculations, but their positions were not refined. Compounds 4 and 5 both crystallized in the monoclinic crystal system. The space groups P2da and P21fc, respectively, were identified uniquely on the basis of the patterns of systematic absences observed during the collection of the intensity data. Both structures were solved by a combination of direct methods (MITHRIL) and difference Fourier syntheses. All non-hydrogen atoms were refined with anisotropic thermal parameters. The positions of the hydrogen atoms on the 9S3 ligand were calculated by assuming idealized tetrahedral eometries at the carbon atoms with C-H distances of 0.95 . The scattering contributions of the hydrogen atoms were included in the structure factor calculations, but their positions

1

1742 Organometallics, Vol. 14,No.4, 1995

Adams et al.

Table 2. Positional Parameters and B ( e d Values for 2 0.37109(6) 0.29892(6) 0.14721(5) 0.22738(6) 0.30070(6) 0.22371(6) 0.3443(2) 0.1404(2) 0.2007(2) 0.5415(6) 0.448 l(6) 0.4616(6) 0.2 I79(6) 0. IOl8(6) 0.0185(6) 0.0298(5) 0.4533(7) 0.2 123(9) 0.3524(6) 0.2803(8) 0.2482(6) 0.057 l(6) 0.2580(7) 0.3463(8) 0.288(I ) 0.198( I ) 0.0884( 7) 0.1355(7) 0.1360(7) 0.2935(8) 0.35 lO(8) 0.4012(7) 0.476 I(9) 0.4164(8) 0.3993(9) 0.2484(7) 0.1 187(8) 0.0678( 8) 0.0837(8) 0.395( 1) 0.246( I ) 0.3303(7) 0.2621(9) 0.2526(7) 0.1217(9) 0.959( I ) 0.932( 1) 0.971(1) 0.459(1) 0.4290(9) 0.472(1)

0.0426( I ) -0. IO0 I ( I ) -0.0221( I ) 0.12 16(I ) 0.1750( 1) -0.1735(1) 0.1806(3) 0.040 l(3) 0.3369(3) 0.166(2) -0.155(1) -0.157( I ) -0.226( I ) 0.071( I ) -0.283(1) 0.108 l(9) 0.402( I ) 0.362( 1) 0.1018(9) -0.330( I ) -0.400( 1) -0.341( 1) 0.010( 1 ) 0.133( I ) 0.006( 1) 0.017( I ) 0.162(1) 0.307(1) 0.378( I ) 0.46% I ) 0.452( 1) 0.356( 1) 0.119(2) -0.083(2) -0.134( I ) -0.179( 1) 0.040( I ) -0.185( I ) 0.068(1) 0.3 17(2) 0.286(2) 0.090( 1) -0.268( 1) -0.288( 1) -0.275( 1) 0.542(2) 0.418(2) 0.379(2) 0.596(2) 0.486(2) 0.390(2)

(A2)

9 1.40(4) Ru(2)-Ru( I)-Ru(4) 57.72 Ru(Z)-Ru( I)-Ru(5) Ru(Z)-Ru( 1)-R~(6) 57.96 141.66(9) Ru(Z)-Ru( 1)-S( I ) R u ( ~ ) - R u ( I)-Ru(5) 62.09(4) Ru(~)-Ru(1)-Ru(6) 64.72(3) 50.55(8) Ru(4)-Ru(l)-S( 1) 90.48(4) Ru(S)-Ru( I)-Ru(6) 94.3( 1) Ru(S)-Ru( I)-S( 1 ) Ru(6)-Ru( I)-S( 1) 101.24(8) Ru(l)-Ru(2)-Ru(3) 87.97(3) Ru( I)-Ru(2)-Ru(5) 60.30(4) Ru( I )-Ru(2)-Ru(6) 60.22(4) 60.50(4) Ru(3)-Ru(2)-Ru(5) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 60.8I(4) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 93.48(4) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 89.26(4) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 58.27(4) Ru(2)-Ru(3)-Ru(6) 58.32(4) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 60.53(4) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 62.86(4) R u ( ~ ) - R u ( ~ ) - R ~ ( ~90.60(4) ) Ru( I ) - R u ( ~ ) - R u ( ~ ) 91.32(4) Ru( I)-Ru(4)-Ru(5) 6 I . 16(4) Ru( 1)-Ru(4)-Ru(6) 59.77(4) Ru( I )- Ru(4)-S( 1) 53.04(8) Ru(l)-Ru(4)-Sf2) I24.0( 1 ) Ru(l)-Ru(4)-S(3) 128.88(9) R~(3)-Ru(4)-Ru(5) 59.26(4) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 58.43(4) Ru(3)-Ru(4)-S( 1) 144.21(8) R~(3)-Ru(4)-S(2) 105.50(7) R~(3)-Ru(4)-S(3) 104.3(I ) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 87.38(4) Ru(S)-Ru(4)-S( I ) 95.2(1) Ru(5)-Ru(4)-S(2) 164.74(7) R~(5)-Ru(4)-S(3) 85.6(1) Ru(6)-Ru(4)-S( I ) 99.1(1) R~(6)-Ru(4)-S(2) 84.37(8) Ru(6)-Ru(4)-S(3) 162.4(1) S( I)-Ru(4)-S(2) 98.7(1) S( I)-Ru(4)-S(3) 97.6(1) 98.5( I ) S(2)-Ru(4)-S(3) Ru( 1 )-Ru(S)-Ru(2) 61.98(4)

0.1604(1) 0.4454( I ) 0.35095(9) 0.07375(9) 0.281 I ( I ) 0.2603 1) -0.0520( 3) -0.0457(3) -0.0172(3) 0.189(1) 0.127(1) 0.540( I ) 0.7299(9) 0.544(1) 0.514(1) 0.1549(9) 0.162( I ) 0.3 IO(2) 0.5555(8) 0.141(1) 0.5248(9) 0.279(I ) 0.256( I ) -0.182( I ) -0.144(1) -0.167( I ) -0.163( I ) -0.238( I ) -0.155( 1) -0.107( I ) -0.198( 1) -0.141(1) 0.179( 1) 0.142(1) 0.500(I ) 0.622( I ) 0.470( I ) 0.45 1( 1) 0.210( I ) 0.205( 1) 0.296(2) 0.465( 1) 0.183 I ) 0.445( I ) 0.273( I ) 0.887(2) 1.000(2) 1.109(2) 0.458(2) 0.447( 1) 0.490(2)

Ru(2)-Ru(5)

Ru( 2)-Ru(6) Ru(2)-C( I ) Ru(3)-Ru(4) Ru(3)-Ru(S) Ru(3)-Ru(6) Ru(3)-C( I ) Ru(4)-Ru(5) Ru(4)-Ru(6) Ru(4)-S(1) Ru(4)-S(2)

2.947(2) 2.768(2) 2.900(2) 2.902(2) 2.276(3) 2.05(1) 2.909(2) 2.823(2) 2.834( I ) 2.11(1) 2.9 16(1) 2.888( I ) 2.907(2) 2.01(1) 2.926( 1) 3.037(2) 2.199(3) 2.357(3)

Ru( I)-Ru(5)-Ru(3) 89.28(5) Ru( 1 )-Ru(5)-Ru(4) 56.75(4) Ru(2)-Ru(S)-Ru( 3) 6 1.24(4) Ru(2)-R~(5)-Ru(4) 90.78(5) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 60.21(4) Ru( 1)-R~(6)-Ru(2) 61.82(4) Ru( I)-Ru(6)-Ru(3) 88.87(5) Ru( I)-Ru(6)-Ru(4) 55.52(3) Ru(l)-Ru(6)-C(I) 45.1(3) Ru( I)-Ru(6)-C(61) 94.6(4) 98.3(3) Ru( 1)-R~(6)-C(62) 162.2(4) Ru( I)-Ru(6)-C(63) 60.87(4) Ru(2)-Ru(6)-Ru(3) 88.32(5) Ru(2)-Ru(6)-Ru(4) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 58.71(4) 76.41(9) Ru(I)-S(l)-Ru(4) 120.6(4) Ru(l)-S( I)-C(2) 118.9(5) Ru(l)-S(l)-C(lO) 118.3(4) Ru(4)-S(I)-C(2) 120.2(5) Ru(4)-S( 1)-C( 10) C(2)-S( I)-C( IO) 102.4(6) R u ( ~ ) - S ( ~ ) - C ( ~ ) 112.1(5) R u ( ~ ) - S ( ~ ) - C ( ~ ) 113.2(5) 98.4(6) C(4)-S(2)-C(5) Ru(4)-S(3)-C(7) 114.6(5) 1 11.1(5) RN4)-S( 3)-C( 8) C(7)-S(3)-C(8) 99.7(6) S( I )-c(2)-c(3) 112(1) C(2)-C(3)-C(4) 11x1) S(2)-C(4)-C(3) 117(1) S(2)-C(5)-C(6) 117.3(9) C(5)-C(6)-C(7) 113(1) S(3)-C(7)-C(6) 118(1) S(3)-C(8)-C(9) 119(I ) C(8)-C(9)-C( IO) 120(1) S( 1)-C(lo)-c(9) I14.7(9) R~(2)-C(53)-Ru(5) 83.1(6) Ru(2)-C(53)-0(53) 129.1(9) R~(5)-C(53)-0(53) 148(I ) Ru(2)-C(62)-Ru(6) 85.7(5) 133(1) R~(2)-C(62)-0(62) 141(1) R~(6)-C(62)-0(62) Ru-C-O(av) 176(1)

('Angles are in degrees. Estimated standard deviations in the least significant figure are given in parentheses.

Table 3. Intramolecular Distances for 2" Ru( 1)-Ru(2) Ru( I)-Ru(4) Ru( I)-Ru(5) Ru( I)-Ru(6) Ru( I)-S( 1) Ru( I)-C( I ) Ru(2)-Ru(3)

Table 4. Intramolecular Bond Angles for 2"

Ru(4)-S(3) Ru(4)-C(I) Ru(S)-C( 1) Ru(6)-C( I ) S( 1)-C(2) S(I)-C(IO) S(2)-C(4)

2.352(3) 1.98(1) 2.06( I ) 2.08(1) 1.81( 1) 1.82(I ) 1.83(1)

W)-W)

1.81(1)

S(3)-C(7) S (3)-C(8) 0-C(av) C(2)-C(3) C(3)-C(4) C(5)-C(6) C(6)-C(7) C(8)-C(9) C(9)-C( IO)

1.83(1) 1.82(1) I . 1x2) 1.45(2) 1.56(2) 1 SO(2) 1.53(2) 1.51(2) 1.44(2)

a general position in the lattice. It was added to the analysis and satisfactorily refined with anisotropic thermal parameters for the carbon atoms. In the final stages of the analysis of compound 5 one formula equivalent of CH2C12 that had cocrystallized from the crystallization solvent was located in a general position in the lattice. It was added to the analysis and satisfactorily refined with anisotropic thermal parameters for the chlorine atoms and an isotropic thermal parameter for the carbon atom.

Results and Discussion The reaction of 12S3 with Rug(C0)17(ug-C), 1, in octane solvent at reflux produced only one compound R~6(C0)&-~~-12S3)(ug-C), 2, in 78%yield. Compound

I' Distances are in angstroms. Estimated standard deviations i n the least significant figure are given in parentheses.

were not refined. In the final stages of the analysis of compound 4 one formula equivalent of benzene that had cocrystallized from the crystallization solvent was located in

2 was characterized by a combination of IR,

'H NMR,

Hexaruthenium Carbido Carbonyl Clusters

Organometallics, Vol. 14, No. 4, 1995 1743

Figure 2. ORTEP diagram of R~s(C0)150A-)7~-16S4)0A6-C), 3, showing 40% probability thermal ellipsoids. Table 5. Positional Parameters and B(eq) Values (biz) for 3 and single crystal X-ray diffraction analysis. An ORTEP drawing of the molecular structure of 2 is shown in atom X v z Neq) Figure 1. Final atomic positional parameters are listed Ru(1) '/4 0.37176(9) 3.19(5) 0.97861(4) 0.16581(4) 0.15828(8) 2.92(3) in Table 2. Selected interatomic distances and angles Ru(2) 1.04277(3) 0.16984(3) 0.15570(8) 3.14(3) Ru(3) 0.91790(3) are listed in Tables 3 and 4, respectively. The molecule '/d -0.0598( I ) 3.02(5) Ru(4) 0.98500(4) contains an octahedral Rue cluster with a carbido ligand S(1) 1.13074(9) 0.16oO( I ) 0.2865(2) 3.4( I ) inside the cluster. This is structurally analogous to that S(2) 1.2316(1) 0.0935(2) 0.7285(3) 5.5(1) '/4 O m ( 1) 6.6(6) of the parent complex 1.8 The 12S3 ligand exhibits a O(11) 0.8713(4) 0.3778(4) 0.5394(7) 6.3(4) p-v3 tridentate coordination. All three sulfur atoms are O(12) 1.0335(3) O(2 1) 1.0964(3) 0.0960(4) -0.0994(7) 6.4(4) coordinated t o one ruthenium atom Ru(41, but one of o(22) 1,0032(3) o,oo74(4) 7.9(5) 0.228( I ) the sulfur atoms S(1) also uses its second lone pair of O(31) 0.8042(4) '/j 0.157( I ) 6.0(5) electrons to coordinate to one of the neighboring rutheO(32) 0.8586(3) 0.0491(4) -0.0163(7) 6.4(4) nium atoms Ru(1) and forms a bridging interaction. A O(33) 0.8703(4) 0.0854(4) 0.4026(8) 9.4(5) O(41) 0.9264(3) 0.3681(4) -0.2419(7) 5.7(4) similarly coordinated 12S3 ligand was found in the o(42) 1,0853(4) 5.9(5) -0.261( I ) complex Ru5(C0)ll(lL-v3-12S3)~5-C), 6, that was recently C(1) 0.9829(5) '/4 0.157( 1) 2.9(5) obtained by us from the reaction of Ru~(CO)&~-C) with C(2) 1.1486(3) 0.0644(5) 0.342( 1) 4.2(4) 12S3 and the compound R U S ( C O ) ~ ~ ~ ~ - ~ ~ - C C(3) O ) ~ - ~1.1964(3) ~0.0632(5) 0.4524(9) 4.1(4) C(4) 1.1775(4) 0.0918(5) 0.5951(9) 4.1(4) 12S3), 7, that was obtained from the reaction of 12S3 C(5) 1.26934) 0.1770(6) 0.685( 1) 5.8(6) with R u ~ ( C O ) ~ Z . ~ '/4 0.699( I ) 5.9(9) C(6) 1.2377(6) The metal-metal bond distances in 2 are similar to C(7) 1.1888(5) '/4 0.088( I ) 4.2(7) 0. I70( I ) 4.4(4) C(8) 1.1914(3) 0.1761(5) those found in 1,but as found in 6, the macrocycle does '/4 0.488( 1) 4.4(7) C(11) 0.9109(6) produce significant effects on these distances. For example, the sulfur-bridged metal-metal bond, Ru(1)Ru(4), is the shortest in the molecule, 2.768(2)A, while the other metal-metal bonds to Ru(4), Ru(3)-Ru(4) = 2.916(1) A, Ru(4)-Ru(5) = 2.926(1) A, and Ru(B)-Ru(6) = 3.037(2)A, are the longest in the molecule. There are two metal-metal bonds that contain bridging carbonyl ligands, Ru(2)-Ru(5) and Ru(2)-Ru(6), and these bonds also have relatively short lengths, 2.823(2) and 2*834(1)A, respectively. The carbid0 ligand does not lie in the exact center of the Rue octahedron but is shifted closer to the metal atom coordinated to the 12S3 ligand (e.g. Ru(4)-C(1) = 1.9&1), Ru(2)-C(1) = 2.11(1)A). A similar shift of the carbido ligand was observed in 6. In 2 , 6, and 7 the 12s3 ligand adopts a conformation in which the three sulfur atoms point toward the inside of the ring to facilitate coordination to the metal atoms. However, this is quite unlike the free molecule andY" mononuclear metal complexes where the lone pairs on the sulfur atoms do not point to the inside of (8)(a) Braga, D.; Grepioni, F.; Dyson, P. J.; Johnson, B. F. G.; Frediani, P.; Bianchi, M.; Piacenti, F. J . Chem. Soc., Dalton Trans. 1992, 2562. (b) Sirigu, A.; Bianchi, M.; Benedetti, E. Chem Commun. 1969, 596.

C(12) c(21) C(22) C(31) C(32) C(33) c(41)

1.0146(4) 1,0761(4) 1.0138(4) 0.8542(5) 0.8812(4) 0.8891(4) o,9471(4)

0.3312(5) o,,258(5) 0.0684(5)

0.0969(5) 0.1 197(5) o,3261(5)

0.4703(9) -o,oo6(1) 0.203( 1) 0.157( I ) 0.045( I ) 0.309( 1) -o,164(1)

C(42)

1.0490(5)

'/J

-0.183( 1)

'/d

4.2(4) 4.2(5) 5.0(5) 3.9(6) 3.9(4) 5.2(6) 4.0(4) 437)

the ring.9 In 2 the 1 2 ~ ligand 3 serves as an 8 electron donor and the cluster attains the expected 86 electron configuration, When exposed to a CO atmosphere in a THF solution for 5 h at 67 o c , compound2 was converted back to 1 in 45% yield by loss of the 1 2 ~ ligand, 3 nus, the 1 2 ~ 3 substitution of 1 is not fully reversible, but the 12S3 ligand can be displaced to a significant degree by co under these mild conditions. The compound 3, was obtained in 58% yield from the reaction of 16S4 with octane solvent at reflux. compound 3 was also characterized by a single crystal X-ray diffraction analysis. (9) ( a ) Rawle, S. C.; Admans, G. A.; Cooper, S. R. J . Chem. SOC., Dalton Trans. 1988,93.

1744 Organometallics, Vol. 14, No. 4, 1995

Adams et al. Table 8. Positional Parameters and B(eq) Values (A2)for 4

Table 6. Intramolecular Distances for 3" Ru(l)-Ru(2) Ru( I)-Ru(3) Ru(l)-C(I) Ru(l)-C(Il) Ru( 1)-C(12) Ru(2)-Ru(2*) Ru(2)-Ru(3) Ru(2)-Ru(4) Ru(2)-S( I ) Ru(2)-C( I ) Ru(2)-C(21) Ru(2)-C(22) Ru( 3)-Ru(3*) Ru(3)-Ru(4) Ru(3)-C(l) Ru(3)-C(3 I )

2.920( I ) 2.861( 1) 2.03( 1 ) l.93( 1) 1.90(1) 2.971(1) 2.9 197(9) 2.878(1) 2.389(2) 2.04 l(8) 1.874(9) 1.90(I ) 2.829( I ) 2.934( 1) 2.076(8) 2.05( I )

1.867(9) l.83( I ) 2.05( I ) 1.89( 1 ) I .90( I ) I .8 14(8) I .8 l9(8) 1.786(9) 1.77(I ) 1.53(1) I .5 1 ( I ) I .49(I ) 1.52(1) 3.18(4) 1.14(1 )

atom

Ru( I ) Ru(2) Ru(3) Ru(4) Ru(5) Ru(6)

0.1885(5) 0.0449(4) 0.3936(4) 0. I547(4) 0.3507(5) 0.5672(4) 0.2784(4) 0.3097(4) 0.012 3 0 ) -0.0204(5) 0.0818(7) 0.1866(7) 0.2075(6) 0.1928(6) 0.4754(5) 0.58 l9(6) 0.403 l(4) 0.423l(6) 0.3390(6) 0.523 l(6) 0.0995(5) 0. I9 14(6) 0.1040(6) 0.3587(5) 0.2 106(6) 0.35 1 3 0 ) 0.4894(6) 0.3037(5) 0.6429(8) 0.5631(8) 0.5322(7) 0.579( 1) 0.6578(9) 0.6890(7)

Table 7. Intramolecular Bond Angles for 3" R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 58.88(3) Ru(2)-Ru(3)-C(3 1 ) 137.9(2) Rt1(2)-Ru(3)-C(32) I16.6(3) Ru(2)-Ru(3)-C(33) IlOS(3) Ru(3)-Ru(3*)-Ru(4) 61.18(2) Ru(3)-R~(3*)-C(31) 46.32) Ru(3)-Ru(3*)-C(32) 133.6(2) Ru(3)-Ru(3*)-C(33) 118.9(3) R u ( ~ ) - R u ( ~ ) - C1)( ~ 93.3(3) Ru(4)-Ru(3)-C(32) 100.9(3) Ru(4)-Ru(3)-C(33) 168.9(3) C(31 )-Ru(3)-C(32) 98.3(4) C(31)-Ru(3)-C(33) 93.6(4) C(32)-Ru(3)-C(33) 86.7(4) R~(2)-Ru(4)-Ru(2*) 62. U(3) R~(2)-Ru(4)-Ru(3) 60.30(2) Ru(2)-Ru(4)-Ru(3*) 90.13(3) R u ( ~ ) - R u ( ~ ) - C ( ~ L ) 164.1(3) Ru(2)-Ru(4)-C(41) 103.1(3) Ru(2)-Ru(4)-C(42) 94.0(3) Ru(3*)-Ru(4)-Ru(3) 57.63(3) Ru(3*)-Ru(4)-C(41) I17.1(3) Ru(3)-Ru(4)-C(41) 76.6(3) Ru(3*)-Ru(4)-(C42) 148.0(2) C(41*)-Ru(4)-C(41) 90.9(5) C(41)-Ru(4)-C(42) 92.9(4) Ru(2)-S( l)-C(2) 112.6(3) Ru(2)-S(l)-C(8) 110.9(3) C(2)-S( 1)-C(8) 98.1(4) C(4)-S(2)-C(5) 101.9(4) S(I)-C(2)-C(3) I12.2(6) C(2)-C(3)-C(4) 1 13.1(7) S(2)-C(4)-C(3) 11536) S(2)-C(5)-C(6) 116.7(7) C(5)-C(6)-C(5*) 119( I ) C(S)-C(7)-C(8*) 119(1) S( I)-C(8)-C(7) 114.3(7) Ru-C-O(av) 175.0(8) Ru(3)-C(3 1)-Ru(3) 87.1(5) R~(3)-C(31)-0(31) 136.5(2)

Angles are in degrees. Estimated standard deviations in the least significant figure are given in parentheses. -

An ORTEP drawing Of the structure Of is shown in Figure 2. Final atomic positional parameters are listed in Table 5. Selected interatomic distances and are listed in and 7, respectively. The lies On a crystallo~aphicreflection plane and thus contains a rigorously imposed reflection symmetry. The atoms R'(l)' c(l)' and Ru(4) and the ligands C(12)-0(12), C(31)-0(31), and C(42)-0(42) lie On the 'lane' This contains an octahedral RusC cluster; however, unlike 2 the 16S4 ligand in 3 is only partially coordinated. Two of the sulfur atoms, S(1)and S(l*),are coordinated to adjacent

0.44354(4) 0.39331(4) 0.19324(4) 0.22377(4) 0.30220(4) 0.34943(4) 0.1377(1) 0.0784( I ) 0.26431) 0.4992(5) 0.6644(4) 0.4248(4) 0.4412(5) 0.3098(6)

S(2) S(3) 0(1I ) O(12) O( 14) O(21) O(22)

'' Distances are in angstroms. Estimated standard deviations in the least significant figure are given in parentheses.

Ru(2)-Ru( 1)-Ru(2*) 61.14(3) Ru(Z)-Ru( I)-Ru(3) 60.66(2) Ru(2)-Ru( I)-Ru(3*) 90.73(3) Ru(2)-Ru(l)-C(I 1 ) 144.7(2) Ru(2)-Ru(l)-C(12*) 119.5(3) Ru(2)-Ru(l)-C(12) 74.2(2) Ru(3)-Ru(I)-Ru(3*) 59.25(3) Ru(3)-Ru(l)-C(lI) 90.1(3) Ru(3)-Ru( 1)-C(12*) 160.1(3) Ru(3)-Ru( I)-C( 12) 101.3(3) C(l l)-Ru( 1)-C(12*) 94.8(4) C( 12)-Ru( I )-C( 12*) 97.5(5) Ru(l)-Ru(2)-Ru(2*) 59.43(2) Ru(l)-Ru(2)-Ru(3) 58.67(3) Ru( I)-Ru(2)-Ru(4) 89.52(3) Ru(l)-Ru(2)-S( I ) 96.49(6) Ru(l)-Ru(2)-C(21) 167.7(3) Ru( I)-Ru(2)-C(22) 97.0(3) R u ( ~ * ) - R u ( ~ ) - R u ( ~ ) 88.61(2) Ru(2*)-Ru(2)-Ru(4) 58.92(2) Ru(2*)-Ru(2)-S(l) 92.46(5) Ru(2*)-Ru(2)-C(21) 112.2(3) Ru(2*)-Ru(2)-C(22) 155.0(3) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 60.81(3) R u ( ~ ) - R u ( ~ ) - S ( I ) 149.95(6) R u ( ~ ) - R u ( ~ ) - C ( ~ I ) 1 14.7(3) Ru(3)-Ru(2)-C(22) 7033) R u ( ~ ) - R u ( ~ ) - S ( I ) 142.136) Ru(4)-Ru(Z)-C(21) 78.3(3) Ru(4)-Ru(2)-C(22) 1 17.5(3) S(I)-Ru(2)-C(?I) 92.7(3) S(I)-Ru(2)-C(22) 98.9(3) C(21)-Ru(2)-C(22) 89.6(4) Ru(l)-Ru(3)-Ru(2) 60.68(3) R u ( ~ ) - R u ( ~ ) - R u ( ~ * )60.37(2) Ru(l)-Ru(3)-Ru(4) 89.56(3) Ru(l)-Ru(3)-C(31) 90.9(3) Ru(l)-Ru(3)-C(32) 165.6(2) Ru(l)-Ru(3)-C(33) 8 1.7(3) R u ( ~ ) - R u ( ~ ) - R u ( ~ * )91.39(2)

t.

Neq)

v

0.03082(3) 0.16749(3) 0.14725(3) 0.00979(3) 0.06848(3) 0.10164(3) -0.02854(9) -0.0096(1) -0.09710(9) -0.0967(3) 0.0384(3) -0.0499(3) 0.281 l(4) 0.2588(3) 0.1724(3) 0.1089(3) 0.2870(3) 0.1648(3) 0.1294(3) 0.0023(3) 0.2203 3) 0.0763(3) 0.0323(3) 0.0839(3) -0.05 13(4) -0.0164(4) -0.0942(4) -0.1203(4) -0.1461(4) -0.1076(4) -0.0487(4) 0.0375(4) -0.0053(4) 0.2368(5) 0.22334) 0.1670(3) 0.12 13(4) 0.2356(4) 0.1572(3) 0.1075(4) 0.0253(4) 0.1756(4) 0.0786(4) 0.0562(4) 0.3 1 13(6) 0.2700(6) 0.2426(4) 0.2573(6) 0.2990(7) 0.3259(5)

0.23765(4) 0.20264(4) 0.261 18(4) 0.26676(4) 0.08465(4) 0.39195(4) 0.4091(1) 0.1748(1) 0.2375(2) 0.3318(4) 0.1906(4) 0.0423(4) 0.3387(6) 0.0421(6) 0.1028(5) 0.4184(4) 0.3317(5) 0.0844(4) -0.1028(4) -0.0577(4) 0.5244(5) 0.4472(4) 0.581 l(4) 0.2401(4) 0.3641(5) 0.2688(5) 0.13 lO(6) 0.1286(7) 0.3396(7) 0.4347(6) 0.2967(5) 0.2059(5) 0.0903(5) 0.2897(7) 0.1002(7) 0.1432(6) 0.3578(6) 0.3019(6) 0.1472(6) -0.0319(6) -0.0024( 5 ) 0.4723(6) 0.4099(5) 0.5057(6) -0.3433(8) -0.3456(8) -0.257( I ) -0.1669(9) -0.166(1) -0.254( 1)

2.97(3) 3.34(3) 2.95(3) 2.57(2) 3.04(3) 2.93(3) 3.32(8) 3.9(1) 4.4( 1) 6.2(3) 6.3(3) 4.4(3) 10.6(5) 9.1(5) 7.0(4) 6.0(3) 7.8(4) 6.5(3) 7.0(4) 6.9(4) 7.4(4) 6.8(3) 5.7(3) 2.4(3) 4.0(4) 4.4(4) 5.7(5) 6.3(5) 5.5(5) 4.7(4) 3.6(4) 4.0(4) 3.1(3) 6.3(5) 5.6(5) 4.3(4) 4.1(4) 4.8(4) 4.0(4) 4.4(4) 4.7(4) 4.4(4) 4.6(4) 3.8(4) 7.0(6) 7.2(7) 6.9(6) 8.4(8) 8.4(8) 7.7(7)

metal atoms, Ru(2) and Ru(2*), Ru(2)-S(l) = 2.389(2) other two sulfur atoms S(2) and S(2*) are uncoordinated. There is no shortening of the 16S4 bridged metal-metal bond in this molecule. In fact, in this case this is the longest metal-metal bond in the molecule, Ru(2)-Ru(2*) = 2.971(1)A. The 16S4 ligand has changed its conformation from that observed in the free In the free m0leCUk two nonadjacent sulfur atoms lie in exo-Dositions at the corners of a rectangular molecule. The other two are endo and lie along the edges of the rectangle; see the diagram in the Introduction. In 3 two adjacent sulfur atoms have endoconfigurations and are coordinated to the two ruthenium atomsof the cluster while the twouncoordinated sulfur atomshave exo-configurations. This appears to be a newly observed conformation of this ligand and is undoubtedly a consequence of directing influences from its coordination to the cluster, Note, the distance between the two coordinated sulfur atoms is 3.176(4)A

A. The

-

(10) Blake, A. J.; Gould, R. 0.;Halcrow, M. A,; Schroder, M. Acta Crystallogr. 1993,B 4 9 , 7 7 3 .

Hexaruthenium Cai-bid0 Carbonyl Clusters

Organometallics, Vol. 14, No. 4, 1995 1745

noS2

C6

Figure 3. ORTEP diagram of R~s(C0)~4(11~-9S3)(~6-C), 4, showing 40% probability thermal ellipsoids, Table 9. Intramolecular Distances for 4 O

Table 10. Intramolecular Bond Andes for 4" ~~~~

Ru( I)-Ru(2) Ru( I)-Ru(4) Ru( I)-Ru(5) Ru( I)-Ru(6) Ru( 1)-C( I ) Ru(2)-Ru(3) Ru(2)-Ru(5) Ru(2)-Ru(6) Ru(2)-C( I ) Ru(3)-Ru(4) Ru(3)-Ru(5) Ru(3)-Ru(6) Ru(3)-C( 1) Ru(4)- Ru(5 ) Ru(4)-Ru(6) Ru(4)-S( I )

2.948( 1) 2.9988(8) 2.8413(8) 2.8049(9) 2.10 1(6) 2.822 l(8) 2.8331(9) 2.8913(9) 2.123(6) 2.882( I ) 3.1926(9) 2.8419(8) 2.059(6) 2.8814(9) 3.0088(8) 2.338(2)

2.306(2) 2.316(2) I .954(6) 2.056(6) 2.079(6) I .830(7) I .826(7) 1.821(7) I . 846(8) 1.817(9) 1.848(8) 1.140(8) 1.50( 1) 1.50( I ) 1.49(I )

' I Distances are in angstroms. Estimated standard deviations in the least significant figure are given in parentheses.

~~

Ru(Z)-Ru( 1)-Ru(4) 86.45(2) R u ( ~ ) - R u I)-Ru(5) ( 58.56(2) Ru(2)-Ru( 1)-Ru(6) 60.28(2) 59.05(2) Ru(4)-Ru( I)-Ru(5) Ru(~)-Ru(I)-Ru(6) 62.35(2) Ru(S)-Ru( l)-Ru(6) 93.49(3) Ru(l)-Ru(2)-Ru(3) 9 1.70(2) 58.84(2) Ru(l)-Ru(2)-Ru(5) Ru(l)-Ru(2)-Ru(6) 57.41(2) Ru(3)-Ru(2)-Ru(5) 68.74(2) Ru(3)-Ru(2)- Ru(6) 59.64(2) Ru(5)-Ru(2)-Ru(6) 91.83(3) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 91.13(2) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 55.79(2) R ~ ( ~ ) - R u ( ~ ) - R u ( ~ 61.39(2) ) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 56.36(2) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 63.43(2) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 85.70(2) Ru(1 )-Ru(4)-Ru(3) 89.5 l(2) Ru( 1)-Ru(4)-Ru(5) 57.75(2) Ru( I )-Ru(4)-Ru(6) 55.66(2) 130.02(5) Ru( 1)-Ru(4)-S( I ) Ru( 1)-Ru(4)-S(2) l41.20(5) Ru( I )-Ru(4)-S(3) 83.43(5) R u ( ~ ) - R u ( ~ ) - R ~ ( ~67.28(2) ) Ru(3)-Ru(4)-Ru(6) 57.64(2) Ru(3)-Ru(4)-S( I ) 106.60(5) Ru(3)-Ru(4)-S( I ) 92.36(6) 167.63(6) R~(3)-Ru(4)-S(3) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 88.53(3) Ru(S)-Ru(4)-S( I ) 171. I l(5) 87.53(5) Ru(5)-Ru(4)-S(2) R u ( ~ ) - R u ( ~ ) - S ( ~ ) 100.35(5) 93.45(5) Ru(6)-Ru(4)-S( I ) 148.64(6) RN6)-Ru(4)-S(2)

~

R u ( ~ ) - R u ( ~ ) - S ( ~ ) 124.4l(5) S(l)-Ru(4)-S(2) 86.28(6) S(I)-Ru(4)-S(3) 85.68(7) S(2)-Ru(4)-S(3) 86.88(7) Ru( l)-Ru(5)-Ru(2) 62.60(2) Ru( l)-Ru(5)-Ru(3) 86.47(2) Ru( I)-Ru(5)-Ru(4) 63.20(2) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 55.47(2) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 90.91(3) R u ( ~ ) - R u ( ~ ) - R ~ ( ~ 56.36(2) ) R U ( I ) - R U ( ~ ) - R U ( ~ ) 62.3 l(3) Ru(l)-R~(6)-Ru(3) 94.33(3) Ru(l)-Ru(6)-Ru(4) 61.99(2) Ru(2)-Ru(6)-Ru(3) 58.97(2) Ru(2)-R~(6)-Ru(4) 87.29(3) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 58.93(2) Ru(4)-S( I)-C(2) 106.9(2) Ru(4)-S( 1)-C(7) I04.4(3) C(2)-S(I)-C(7) 101.1(3) 106.0(2) Ru(4)-S(2)-C(3) Ru(4)-S(2)-C(4) 107.7(3) C(3)-S(2)-C(4) 99.0(4) Ru(4)-S(3)-C(5) 104.4(3) Ru(4)-S(3)-C(6) I07.9(3) C(5)-S(3)-C(6) 100.5(4) S(l)-C(2)-C(3) 113.5(5) S(2)-C(3)-C(2) 113.0(5) S(2)-C(4)-C(5) I12.0(5) S(3)-C(5)-C(4) I14.4(6) S(3)-C(6)-C(7) II135) S( I)-C(7)-C(6) 112.7(5) Ru-C-O(av) 176.5(8) Ru(l )-C(14)-Ru(5) 85.9(3) Ru(l)-C(14)-0( 14) 135.2(5) RN5)-C( 14)- O(14) 138.6(5)

and the distance between the two ruthenium atoms is 2.971(1) A. Interestingly, although it is the endo sulfurs S(1) and S(1*)that are metal coordinated, the coordination involves the lone pairs of electrons that point away from the interior of the ring. Coordination to the two interior lone pairs would probably generate severe steric interactions between some of the carbonyl ligands and the remainder of the 16S4 ring. Studies have shown that when the 16S4 ligand is coordinated to a single metal atom, the metal generally lies inside the ring and all four of the sulfur atoms adopt endoc o n f i g ~ r a t i o n s . ~ ~The J ~ -carbido ~~ carbon lies almost exactly in the center of the RUGcluster in this molecule. There is one bridging carbonyl ligand C(31)-0(31), and

Angles are in degrees. Estimated standard deviations in the least significant figure are given in parentheses.

(11)Pett, V. B.; Diaddario, J r . L. L.; Dockal. E. R.; Corfield, P. W.; Ceccarelli, C.; Glick, M. D.; Ochrymowycz, L. A,; Rorabacher, D. B. Znorg. Chem. 1983,22, 3661. (12)Jones, T. E.; Sokol, L. S. W. L.; Rorabacher, D. B.; Glick, M. D. J . Chem. SOC.,Chem. Commun. 1979, 140. (13)Craael, J.. Jr.; Pett, V. B.; Glick, M. D.; DeSimone, R. E. Znorg. Chem. 197& 17,2885. (14) DeSimone, R. E.; Glick, M. D. Znorg. Chem. 1978, 17, 3574.

the associated metal-metal bond Ru(3)-Ru(3*) is the shortest in the cluster, 2.829(1) A. The reaction of 9S3 with 1 in hexane solvent at reflux produced the compound R u s ( C O ) ~ ~ ( ~ ~ - ~4,S in ~)~~-C), 93% yield. Compound 4 was also characterized by a single crystal X-ray diffraction analysis, and an ORTEP

I(

Adams et al.

1746 Organometallics, Vol. 14, No. 4, 1995 c3

042 022

032

08011 % o

0 31

Figure 4. ORTEP diagram of R u ~ ( C O ) ~ ~ ~ ~ - ) ~ ~ - S C H Z C H ~ C H 5, ~showing S ) C U 40% ~ . Cprobability ), thermal ellipsoids. drawing of its molecular structure is shown in Figure 3. Final atomic positional parameters are listed in Table 8. Selected interatomic distances and angles are listed in Tables 9 and 10, respectively. This molecule also contains an octahedral Rug cluster with a carbido ligand inside the cluster. The 9S3 ligand exhibits a r3tridentate coordination with all three sulfur atoms coordinated to one ruthenium atom, Ru(4). In this regard the molecule is very similar t o 2, but unlike 2 where one of the sulfur atoms uses its second lone pair of electrons to coordinate t o one of the neighboring ruthenium atoms, in 4 this interaction has not developed. In this case the 9S3 ligand is simply a sixelectron donor. As a result, the cluster contains one more carbonyl ligand than 2 to make up for the lack of donation due to the absence of the bridging interaction. One of the metal-metal bonds is unusually long, Ru(3)-Ru(5) = 3.1926(9)A. There seems to be no simple explanation for this in terms of steric or electronic effects. The shortest metal-metal bond is Ru(1)-Ru(6) a t 2.8049(9) A, and there seems to be no simple explanation for this either. As in 2, the carbido ligand is displaced from the center of the Rug octahedron toward the metal atom containing the 9S3 ligand, Ru(4)-C(1) = 1.954(6)A vs Ru(2)-C(1) = 2.123(6)A. The molecule contains one bridging carbonyl ligand C( 14)O(14). All the others are normal terminal ligands. The ‘H NMR spectrum of 4 has the form of a M B B ’ spectrum with multiplets at 2.78 (6H) and 2.33 (6H) ppm and three coupling constants, 2 J ~ = -13.9 - ~ Hz, 3 5 ~=-7.0 ~ Hz, 3 J ~ =- 6.7 ~ Hz, that were fitted by computer simulation. Since the molecule has no symmetry in the solid state, this indicates that, in solution, it is probably undergoing dynamical rearrangements that lead to an averaging of the three ethylene groups in the 9S3 ligand. It seemed likely that the 9S3 analogue of 2 could be prepared by a simple decarbonylation of 4. In an attempt to prepare such a species, a solution of 1 and 9S3 in octane solvent was heated to reflux for 2 h. From

this reaction the new compound Rus(C0)1&-);r3-SCH26, was isolated in 36% yield. CH~SCH&H~S)(U&),

Compound 5 was characterized by a single crystal X-ray diffraction analysis, and an ORTEP drawing of its molecular structure is shown in Figure 4. Final atomic positional parameters are listed in Table 11. Selected interatomic distances and angles are listed in Tables 12 and 13, respectively. As can be seen, compound 5 is not the 953 analogue of 2. It does not even contain an octahedral Rug carbido cluster. In fact, it does not even contain a 9S3 ligand. The molecule does contain a “spiked” square pyramidal cluster of six ruthenium atoms and one carbido ligand. The carbido ligand lies in the center of the square base as is typical of M5C clusters. The sixth metal atom Ru(4) is linked to one of the metal atoms in the square base, Ru(l), by a single metal-metal bond and bridging interactions to a 3-thiapentane-1,5-dithiolato ligand. The latter was evidently formed from the 9S3 ligand by the elimination of ethylene. Indeed, the formation of ethylene was confirmed by ‘H NMR spectroscopyafter heating a sample of 4 in an NMR tube in toluene-& solvent at 105 “C. From this reaction, 5 was obtained in an even better yield, 68%. The elimination of ethylene from ethanedithiolato ligands15 and ethylene-linked thioethers16 has been observed previously. A 3-thiapentane-1,5-dithiolato ligand was found in the complex Ru~(CO)S(U~-)~~SCH2CH2SCH2CH2S), 8 , which was formed by the (15)McKenna, M.; Wright, L. L.; Miller, D. J.; Tanner, L.; Haltiwanger, R. C.; Rakowski DuBois, M. J . Am. Chem. SOC.1983,105, 5329. (16)Adams, R. D.; Yamamoto, J. H. Znorg. Chim. Acta, in press.

Hexaruthenium Carbido Carbonyl Clusters

Organometallics, Vol. 14, No. 4, 1995 1747

Table 11. Positional Parameters and B(eq) Values (A2)for 5 atom

X

v

Z

B(eq)

0.32525(4) 0.27874(4) 0.2 I 1 17(4) 0.19741(4) 0.15779(4) 0.35234(4) 0.7075(3) 0.8588(3) 0.3104( I ) 0.0903 1) 0.345 I ( I ) 0.2782(5) 0.5 198(4) 0.45 13(5) 0.14 lO(6) 0.3362(5) 0.3569(4) 0.0699(5) 0.0885(4) 0.0516(5) 0.1449(5) -0.0373(4) 0.0890(5) 0.5749(4) 0.3517(5) 0.2895(4) 0.2472(5) 0.1496(5) 0.4029(5) 0.4393(6) 0.29 15(5) 0.4469(6) 0.3842(6) 0.1904(7) 0.3152(6) 0.3020(5) 0.12 13(6) 0.1346(5) 0.1065(6) 0.1673(5) 0.0377(5) 0.1223(6) 0.4909(6) 0.3512(5) 0.793(2)

0.07359(3) 0.03792(4) 0.1585 l(3) -0.06293(3) -0.01336(3) -0.07036(3) 0.0516(3) -0.0736(2) -0.1459( I ) -0.1264(1) -0.0035( I ) 0.2 199(4) 0.1535(4) 0.1508(4) 0.1050(4) -0.1032(4) 0.3018(4) 0.2375(4) 0.2373(4) 0.0720(4) -0. I816(4) 0.0803(3) -0.1054(4) -0.065 l(4) -0.2328(4) 0.047 l(4) -0.2462(4) -0.2283(4) -0.1712(5) -0.0883(5) 0.1647(5) 0.1206(5) 0.1077(5) 0.0830(5) -0.0530(5) 0.2488(5) 0.2059(5) 0.2080(5) 0.0224(5) -0.1383(5) 0.0488(4) -0.0659(5) -0.0665(5) -0.1689(5) -0.0 13( 1)

0.79432(3) 0.541 17(3) 0.66 I56(4) 0.86282(3) 0.67653(3) 0.676 I3(3) 0.8443(3) 0.8665(5 ) 0.795 I( 1) 0.757 I ( 1) 0.9254( I ) 0.9153(4) 0.7629(5) 0.5066(4) 0.3947(4) 0.4174(4) 0.6486(5) 0.5263(4) 0.8014(4) 0.9179(5) 1.0075(4) 0.6883(4) 0.5 146(4) 0.6887(4) 0.5676(4) 0.6713(4) 0.7764(5) 0.7287(5) 0.8770(4) 0.9 17 l(5) 0.8703(5) 0.7762(5) 0.5169(5) 0.4504(5) 0.4670(5) 0.6527(5) 0.5743(6) 0.7510(5) 0.8991(5) 0.9536(5) 0.6861(4) 0.5710(5) 0.6848(5) 0.6066(4) 0.808( 1)

2.81(2) 3.17(2) 3.16(2) 3.00(2) 2.58(2) 2.58(2) 12.8(3) 15.8(3) 2.90(7) 3.22(7) 3.77(8) 7.3(4) 7.3(4) 7.1(4) 7.7(4) 7.0(4) 7.8(4) 6.8(3) 6.0(3) 6.7(4) 7.2(4) 5.4(3) 7.3(4) 6.4(3) 6.0(3) 2.8(3) 3.7(3) 3.9(3) 4.0(3) 4.8(4) 4.3(4) 4.3(4) 4.4(4) 5.0(4) 4.7(4) 4.4(4) 4.7(4) 4.3(4) 4.6(4) 4.2(4) 333) 4.0(3) 3.9(3) 3.7(3) 16.9(7)

reaction of 9S3 with R u ~ C O in ) ~THF ~ s01vent.l~All three sulfur atoms of the 3-thiapentane-1,5-dithiolato ligand are coordinated, and each serves as a bridge between the Rug cluster and the Ru(4) spike. The thioether sulfur S(1) bridges the nonbonded pair Ru(4) and Ru(6). The thiolato sulfur S(2) bridges the nonbonded pair Ru(4) and Ru(51,and the thiolato sulfur S(3) bridges the bonded pair Ru(1) and Ru(4). The thiapentanedithiolato ligand serves as a 10 electron donor in this molecule. Overall the complex contains a total of 90 valence electrons which is in accord with the polyhedral skeletal electron pair theory and the effective atomic number rule.18 Interestingly, the loss of ethylene from complex 4 is more facile than loss of CO which should have produced a stable species analogous to 2. In contrast, the reaction of 1 with 12S3 proceeds to 2 because the formation of a (17)Rossi, S.; Kallinen, K.; Pursianinen, J.; Pakkanen, T . T.; Pakkanen, T. A. J. Organomet. Chem. 1992,440, 367. (18) Mingos, D. M. P.; May, A. S.In The Chemistry ofMetal Cluster Complexes; Shriver, D. F., Kaesz, H. D., Adams, R. D., Eds.; VCH Publishers: New York, 1990; Chapter 2.

Table 12. Intramolecular Distances for 5" Ru(l)-Ru(3) Ru(1 )-Ru(4) Ru(lf-Ru(5) Ru( I)-Ru(6) Ru(I)-S(3) Ru( I)-C( I ) Ru( I )-C( I 1) Ru( 1)-C( 12) Ru(2)-Ru(3) Ru(2)-Ru(5) Ru(2)-Ru(6) Ru(2)-C( I ) Ru(2)-C(21) Ru(2)-C(22) Ru(2)-C(23) Ru(3)-Ru(5) Ru(3)-C( I ) Ru(3)-C(3 1) Ru(3)-C(32) Ru(3)-C(33) Ru(4)-S( I )

2.8521(8) 2.9800(9) 3.1699(8) 2.9309(8) 2.366(2) I .992(7) 1.906(8) I .850(8) 2.83 lO(9) 2.8390(9) 2.8374(8) 2.013(7) 1.854(9) 1.934(9) I .899(9) 2.7925(9) 2.048(6) 1.893(8) 1.926(9) 1.92(I ) 2.303(2)

Ru(4)-S(2) Ru(4)-S(3) Ru(4)-C(41) Ru(4)-C(42) Ru(5)-Ru(6) Ru(5)-S(2) Ru(S)-C(I) Ru(5)-C(51) Ru(5)-C(52) Ru(6)-S( I ) Ru(6)-C(I) Ru(6)-C(61) Ru(6)-C(62) S(I)-C(2) S( 1)-C(4) S(2)-C(3) %3)-C(5) C(2)-C(3) C(4)-C(5) 0-C(av)

2.364(2) 2.390(2) 1.9I7(9) 1.882(8) 2.8044(8) 2.369(2) 2.044(6) 1.914~3) 1.872(8) 2.28 l(2) 2.022(6) I .892(8) 1.870(8) 1.820(7) 1.811(7) 1.858(7) I .88 I ( 8) I .55( I ) 1.52(1) I . 130(8)

'' Distances are in angstroms. Estimated standard deviations in the least significant figure are given in parentheses. Table 13. Intramolecular Bond Angles for 5" Ru(3)-Ru( I)-Ru(4) I06.12(2) 106.12(2) R u ( ~ ) - R u 1)-Ru(5) ( 89.23(2) Ru(3)-Ru( 1)-Ru(6) 153.36(5) Ru(3)-Ru(l)-S(3) Ru(4)-Ru( 1)-Ru(5) 58.55(2) Ru(~)-Ru(l)-Ru(6) 76.43(2) Ru(4)-Ru( 1)-S(3) 51.55(5) 54.56(2) Ru(S)-Ru( l)-Ru(6) 109.20(5) Ru(S)-Ru( 1)-S(3) 97.56(5) Ru(6)-Ru( 1)-S(3) R u ( ~ ) - R u ( ~ ) - R ~ ( ~59.01(2) ) 9 1S ( 2 ) Ru(3)-Ru(2)-Ru(6) 59.21(2) Ru(5)-Ru(2)-Ru(6) Ru( l)-Ru(3)-Ru(2) 88.93(2) Ru( I)-Ru(3)-Ru(5) 68.32(2) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 60.64(2) 79.95(5) Ru(l)-Ru(4)-S( I ) 114.06(5) Ru( I)-Ru(4)-S(2) Ru(1)-Ru(4)-S(3) 50.83(5) 8 1.68(6) S(I)-Ru(4)-S(2) 80.24(7) S( I )-Ru(4)-S(3) 158.35(7) S(2)-Ru(4)-S(3) Ru(I)-Ru(5)-Ru(2) 82.79(2) 56.73(2) Ru(l)-R~(5)-Ru(3) Ru(l)-Ru(S)-Ru(6) 58.38(2) 107.67(5) Ru(I)-Ru(5)-S(2) RN2)-Ru(5)-Ru(3) 60.35(2) R u ( ~ ) - R u ( ~ ) - R u ( ~ )60.36(2)

R~(2)-Ru(5)-S(2) 148.16(5) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 93.06(2) Ru(3)-Ru(5)-S(2) 150.26(5) Ru(6)-Ru(5)-S(2) 98.85(5) Ru( 1)-Ru(6)-Ru(2) 87.27(2) Ru(1 )-Ru(6)-Ru(5) 67.06(2) 1 ) Ru(1)-Ru(6)-S( 8 1.370) R u ( ~ ) - R u ( ~ ) - R u ( ~ ) 60.42(2) Ru(2)-Ru(6)-S( 1) 144.01(5) 83.76(5) Ru(S)--Ru(6)-S( 1) Ru(4)-S(l)-Ru(6) 105.83(7) Ru(4)-S( 1 )-C(2) 104.1(3) Ru(4)-S( I)-C(4) 106.0(3) Ru(6)-S( 1)-C(2) 117.1(2) Ru(6)-S( 1)-C(4) I19.3(3) C(2)-S( 1)-c(4) 103.0(3) R~(4)-S(2)-Ru(5) 79.04(6) Ru(4)-S(2)-C(3) I05.9(2) 109.2(3) Ru(5)-S(2)-C(3) Ru( l)-S(3)-Ru(4) 77.61(6) Ru(l)-S(3)-C(5) 110.8(3) Ru(4)-S(3)-C(5) 106.2(3) S( 1)-c(2)-c(3) 107.8(5) S(2)-C(3)-C(2) 114.5(5) I07.7(5) 5(1)-C(4)-C(5) S(3)-C(5)-C(4) 114.2(5) Ru-C-O(av) 175.9(7)

Angles are in degrees. Estimated standard deviations in the least significant figure are given in parentheses.

4-heptane-1,7-dithiolatoligand would require the loss of a trimethylene group which is a much less stable fragment than ethylene.

Acknowledgment. This research was supported by the Office of Basic Energy Sciences of the US.Department of Energy. Supplementary Material Available: Tables of hydrogen positional and thermal parameters and anisotropic thermal parameters (12pages). Ordering information is given on any current masthead page.

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