Barclay, Tosha M.

Cordes, A. W.

Draganjac, Mark

Nave, Paul M.

English

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Journal of the Arkansas Academy of ScienceVolume 53 Article 271999Synthesis and Molecular Structure of[CpRu(PPh3)(pms)2]OTf1.3/4 C2>H4C12Paul M. NaveArkansas State UniversityMark DraganjacArkansas State UniversityA. W. CordesUniversity of Arkansas, FayettevilleTosha M. BarclayUniversity of Arkansas, FayettevilleFollow this and additional works at: http://scholarworks.uark.edu/jaasPart of the Physical Chemistry CommonsThis article is available for use under the Creative Commons license: Attribution-NoDerivatives 4.0 International (CC BY-ND 4.0). Users are able toread, download, copy, print, distribute, search, link to the full texts of these articles, or use them for any other lawful purpose, without asking priorpermission from the publisher or the author.This General Note is brought to you for free and open access by ScholarWorks@UARK. It has been accepted for inclusion in Journal of the ArkansasAcademy of Science by an authorized editor of ScholarWorks@UARK. For more information, please contact scholar@uark.edu, ccmiddle@uark.edu.Recommended CitationNave, Paul M.; Draganjac, Mark; Cordes, A. W.; and Barclay, Tosha M. (1999) "Synthesis and Molecular Structure of[CpRu(PPh3)(pms)2]OTf1.3/4 C2>H4C12," Journal of the Arkansas Academy of Science: Vol. 53 , Article 27.Available at: http://scholarworks.uark.edu/jaas/vol53/iss1/27»>»>>??»»?i?»???»»??•??147Synthesis and molecular structure of [CpRu(PPh 3) (pms) 2]lOTfl*3/4 C2H4Cl2Paul M.Nave*, M.DraganjacDepartment of Chemistry and PhysicsArkansas State UniversityState University, AR 72467A. W. Cordes, Tosha M.BarclayDepartment of Chemistry and BiochemistryUniversity of ArkansasFayetteville, AR 72701*Corresponding AuthorThe cyclooligomerization of thietane in the presence ofmetal carbonyl clusters to yield cyclothioethers has beendemonstrated by Adams and coworkers (Adams andFalloon, 1995). The reaction of the cyclothioethers, 1,3-dithi-ane and 1,4-dithiane, on a single metal species was investi-gated by Sabo-Etienne, Chaudret, and coworkers, using theCp*Ru+ moiety (Rondon, et al., 1994). In this paper, wereport the synthesis and molecular structure of the [CpRu(PPI13) (pms)2] OTfl*3/4 C2H4CI2 continuing our studiesof the coordination of sulfur donor ligands toCPRu(PPh 3)2+.Syntheses were carried out under a dry nitrogenatmosphere using Schlenk techniques. All other reagentswere used as purchased without further purification.For the synthesis of [CpRu(PPh 3) (pms) 2]OTfl« 3/4C2H4C12, I, a 0.0506 g (0.0744 mmol) sample of(CpRu(PPh 3) (tht)2]OTfl was dissolved in 3 mL of 1,2-dichloroethane. A large excess (1 mL) of pentamethylenesulfide was added and the solution stirred under nitrogen for5 days. The mixture was evaporated under a stream of nitro-gen and the solid, yellow residue was recrystallized from1,2-dichloroethane. The product was washed with hexaneand dried. Yield =0.0364 g, 57.1%.[CpRu(PPh 3) (tht)2]OTfl was prepared from[CpRu(PPh 3)2(tht)] OTF1 (Jiang, et al., 1996) by dissolvingapprox. 1.0 g (1.1 mmol) of [CpRu(PPh 3)2(tht)]OTfl in 20mLof tetrahydrothiophene, THT.The mixture was refluxedfor 2.5 hr. Upon cooling, [CpRu(PPh 3)(tht)2]OTfl precipi-tated from solution. The yellow product was filtered,washed with 50:50 hexane:CH 2Cl2 solution and dried.Yield=0.5678 g, 46.1%.The X-Ray structure analysis of[CpRu(PPh 3)(pms)2]OTfl« 3/4 C2H4C12, I, is describedbelow. A crystal ofI(isolated from the reaction flask) wasmounted in a glass capillary. The crystallographic data aregiven in Table 1. Data were collected at ambient tempera-ture on an Enraf-Nonius CAD-4 diffractometer using MoKoc(X=0.71073 A)graphite-monochromated radiation. Atotal of6884 unique reflections was collected using the e-2e scantechnique to a maximum 2e value of 50°. Absorption cor-rections were made using psi scans data from three reflec-tions. The instrument factor p in the weighting expressionW"1=[02(I) + pi2] /4F 2 was 0.05.The structure was solved by the Patterson method andrefined by fullmatrix least-squares. Allprograms used forthe solution and refinement were those of the NRC386 (PCversion of NRCVAX)package (Gabe, et al., 1989). Allnon-H atoms were refined with anisotropic displacement para-meters except the C atoms of the solvate molecule. H atomswere constrained to idealized positions (C-H =0.95 A) withisotropic thermal parameters Uequal to 0.01 plus the Uofthe attached C atom. The solvate molecule was modeled at0.75 occupancy. The maximumshift for the last cycle of full-matrixleast-squares was 0.00 sigma.Final atomic coordinates and equivalent thermal para-meters for the non-hydrogen atoms are given in Table 2.Selected bond distances and angles are given in Table 3.Dissolution of CpRu(PPh 3)(tht)2+ in PMS/1,2-dichloroethane with stirring yields the compound[CpRu(PPh 3) (pms) 2]OTfl- 3/4 C2H4C12,I.The structureofIis seen in Fig. 1. The Ru-S distances of 2.363(2) and2.362(2)A inIare comparable to the Ru-S distances of2.365(3)A in (CpRu(PPh 3)2(pms)]OTfl. These distances areslightly longer than the Ru-S distance of 2.3459(20)A in thethietane complex, (CpRu(PPh 3)2 (SC3H6)]S03CF3 (Park etal., 1994). In the Os-octaethylporphyrin complexes,Fig. 1ORTEP plot of the cation ofI(30% probability ellip-soids) showing atom labeling scheme. Hydrogen atoms areomitted for clarity.Journal of the Arkansas Academy of Science, Vol. 53, 1999147Journal of the Arkansas Academy of Science, Vol. 53 [1999], Art. 27Published by Arkansas Academy of Science, 1999148Table 1. Crystal and Refinement Data for [CpRu(PPh 3)(pms) 2]OTf1-3/4 C2H4C12.formula RuPSsFgOaCs^H^Cl^fw 856.12size, mm 0.10, 0.22, 0.48a, A 11.033(4)b, A 11.4395(18)c, A 16.582(2)a, deg 75.858(13)P, deg 81.48(2)y,deg 75.960(18)V, A 1960.1(8)29 for cell 16-19dcab gcm"3 L45space group Pj7 9F000 877.7abs coef, mm 1 0.732Q max, deg 50h, k,1ranges 0, 13-13, 13-19, 19std refl -4, 0, -3-3, 2, -2-2, -3, 3stds drift,% 1.1absorp range 0.87 - 1.00refl meas 7278unique refls 6884R for merge 0.022I>3a(I) data 3758parameters 432R(F2) 0.052Rw(F2) 0.072GOF 1.10diffmap, eA 3 -0.36(107), 0.76(10)Os(OEP)(pms) 2 and [Os(OEP)(pms) 2]PF6, the Os-S dis-tances are 2.352(2) and 2.382(2)A, respectively (Scheidt andNasri, 1995). Slightly longer M-S distances (range: 2.401 to2.418 A) are observed in the tris-u-pms compound, C13W (u-pms) 3WCl3 (Boorman et al., 1998).As expected, the pms rings are in the chair configura-tion. The distances and angles (Table 3) in these sulfur lig-ands are typical.The significance of complex Imay prove important asa precursor for the preparation of other Ru complexes withweak donor ligands. Ifpentamethylene sulfide can displacetht from the CpRu(PPh 3) (tht) 2+ moiety, similar substitu-tions using (CpRu(PPh 3) (pms) 2]OTfl should be possible.Acknowledgments. —Funding for RuCl3 was providedby the A.S.U. Faculty Research Committee andTable 2. Atomic Parameters (x, y, z) and Beq for[CpRu(PPh 3) (pms) 2]OTfl-3/4 C2H4C12. E.S.D.'s refer tothe last digit printed.x y z Biso/BeqRu 0.05056(6) 0.29895(6) 0.22157(4) 2.93 (3)P 0.01141(19) 0.18333 (17) 0.13496(13) 2.85 (9)51 -0.02942(19) 0.17440(18) 0.34380(13) 3.26 (9)52 0.24444(19) 0.15705(19) 0.24074(14) 3.53 (10)53 0.5117 ( 3) 0.5185 ( 3) 0.2728 ( 2) 5.70 (15)Fl 0.5368 (11) 0.7403 ( 9) 0.2686 ( 7) 12.6 ( 7)F2 0.3920 (11) 0.7360 ( 9) 0.2050 ( 7) 13.6 ( 7)F3 0.3739 (12) 0.6966 ( 9) 0.3349 ( 7) 15.5 ( 8)01 0.4090 (10) 0.4698 (11) 0.2698 ( 8) 12.2 ( 8)02 0.5710 (11) 0.4738 (10) 0.3458 ( 7) 11.5 ( 7)03 0.5947 (12) 0.5257 (10) 0.2012 ( 8) 13.8 ( 8)Cl 0.0190 (13) 0.4714 ( 8) 0.2684 ( 7) 6.0 ( 6)C2 0.1260 (10) 0.4639 ( 8) 0.2153 ( 9) 5.7 ( 6)"C3 0.0965 (14) 0.4651 ( 9) 0.1364 ( 8) 6.5 ( 7)C4 -0.0262 (14) 0.4701 ( 9) 0.1395 (10) 6.7 ( 7)C5-0.0816 (10) 0.4753 ( 8) 0.2198 (10) 6.1 ( 7)C6 -0.0488 (10) 0.2512 (10) 0.4297 ( 6) 5.5 ( 6)C7 -0.1124 (12) 0.1815 (11) 0.5092 ( 6) 6.6 ( 7)C8 -0.2446 (10) 0.1776 (10) 0.4962 ( 6) 5.8 ( 6)C9 -0.2506 (11) 0.1140 (12) 0.4266 ( 7) 6.6 ( 7)C10 -0.1948 ( 8) 0.1790 ( 9) 0.3432 ( 6) 4.7 ( 5)Cll -0.0221 ( 7) 0.0289 ( 6) 0.1805 ( 5) 2.8 ( 3)C12 0.0591 ( 8) -0.0561 ( 8) 0.2346 ( 6) 4.0 ( 4)C13 0.0330 (10) -0.1719 ( 8) 0.2715 ( 6) 4.9 ( 5)C14-0.0729 (11) -0.2011 ( 8) 0.2558 ( 7) 5.4 ( 6)C15 -0.1525 (10) -0.1181 ( 9) 0.2033 ( 7) 5.4 ( 5)C16 -0.1276 ( 9) -0.0053 ( 8) 0.1657 ( 6) 4.3 ( 4)C17 -0.1179 ( 8) 0.2537 ( 7) 0.0682 ( 5) 3.3 ( 4)C18 -0.2283 ( 8) 0.3209 ( 8) 0.1011 ( 6) 4.4 ( 4)C19 -0.3311 ( 9) 0.3682 ( 9) 0.0540 ( 7) 5.2 ( 5)C20 -0.3234 (10) 0.3473 ( 9) -0.0249 ( 7) 5.0 ( 5)C21 -0.2128 ( 9) 0.2820 ( 8) -0.0584 ( 5) 4.1 ( 4)C22 -0.1105 ( 8) 0.2346 ( 7) -0.0118 ( 5) 3.7 ( 4)C23 0.1442 ( 8) 0.1548 ( 7) 0.0577 ( 5) 3.3 ( 4)C24 0.1787 ( 9) 0.2552 ( 8) 0.0017 ( 5) 4.4 ( 4)C25 0.2883 (10) 0.2421 (10) -0.0542 ( 6) 5.4 ( 5)C26 0.3605 ( 9) 0.1267 (11) -0.0553 ( 6) 5.5 ( 6)C27 0.3269 ( 9) 0.0254 ( 9) -0.0009 ( 7) 5.2 ( 5)C28 0.2194 ( 8) 0.0396 ( 8) 0.0543 ( 5) 3.9 ( 4)C29 0.3722 ( 9) 0.2100 (11) 0.1719 ( 6) 5.7 ( 6)C30 0.4966 ( 9) 0.1212 (11) 0.1917 ( 7) 5.7 ( 6)C31 0.5293 ( 9) 0.1135 (10) 0.2790 ( 8) 6.0 ( 6)C32 0.4305 ( 9) 0.0713 (11) 0.3456 ( 6) 5.8 ( 6)C33 0.3019 ( 8) 0.1565 (10) 0.3370 ( 6) 5.0 ( 5)C34 0.4441 (14) 0.6778 (14) 0.2716 ( 8) 7.7 ( 8)Cll 0.1566 ( 4) 0.4619 ( 5) 0.4866 ( 4) 10.2 ( 3)C12 0.3285 ( 6) 0.1894 ( 4) 0.5525 ( 3) 9.6 ( 3)C35 0.3057 (17) 0.4317 (17) 0.5133 (11) 8.0 ( 4)C36 0.3786 (20) 0.3174 (20) 0.5174 (13) 9.5 ( 5)Beq is the Mean of the Principal Axes of the ThermalEllipsoidJournal of the Arkansas Academy of Science, Vol. 53, 1999148Journal of the Arkansas Academy of Science, Vol. 53 [1999], Art. 27http://scholarworks.uark.edu/jaas/vol53/iss1/27?149VpJ•#*rfTable 3. Selected Bond Distances and Angles for [CpRu(PPh 3) (pms) 2]OTFl- 3/4 C2H4C12.Distances (A) Angles (°)Ru-P 2.321 (2) P-Ru-Sl 93.27 (7)Ru-Sl 2.363 (2) P-Ru-S2 87.47 (8)Ru-S2 2.362 (2) Sl-Ru-S2 86.26 (8)Ru-Cl 2.224 (9) Ru-Sl-C6 109.1 (4)Ru-C2 2.215 (9) Ru-Sl-CIO 112.2 (3)Ru-C3 2.193 (9) C6-S1-C10 95.9 (5)Ru-C4 2.154 (10) Ru-S2-C29 112.5 (4)Ru-C5 2.180 (9) Ru-S2-C33 111.0 (3)S1-C6 1.811 (9) C29-S2-C33 96.7 (5)S1-C10 1.813 (9) S1-C6-C7 111.9 (7)S2-C29 1.805 (10) C6-C7-C8 110.9 (9)S2-C33 1.802 (9) C7-C8-C9 113.9 (8)C6-C7 1.533 (15) C8-C9-C10 111.2 (9)C7-C8 1.517 (18) S1-C10-C9 112.1 (7)C8-C9 1.524 (16) S2-C29-C30 110.6 (7)C9-C10 1.521 (14) C29-C30-C31 112.6 (9)C29-C30 1.522 (15) C30-C31-C32 112.0 (8)C30-C31 1.519 (16) C31-C32-C33 113.1 (9)C31-C32 1.509 (15) S2-C33-C32 110.3 (7)C32-C33 1.518 (13)Competitive Applied Research Grant. We thank Mrs. BettyPulford for assistance in the manuscript preparation.Supplementary Material AvailableGabe, E.J., Y.LePage, J. P. Charland, F. L.Lee, and P.S. White. 1989. NRCVAX-an interactive program systern for structure analysis. J. Appl. Cryst. 22:384-387.Jiang, Y., M. Draganjac, and A. W. Cordes. 1996.Molecular structure of [CpRu(PPh 3)2(tht)]BF4, tht =tetrahydrothiophene. J. Cryst. Chem. 26:657-660.Park, H., M.Draganjac, S. R. Scott, A. W. Cordes, andG. Eggleton. 1994. The reaction of CpRu(PPh 3)2+with trimethylenesulfide. Synthesis and molecular andcrystal structure of [CpRu(PPh 3)2(SC3H6)]CF3SO3.Inorg. Chim. Acta 221:157-160.Rondon, D., J. Delbeau, X.-D. He, S. Sabo-Etienne, andB.Chaudret. 1994. Activation of carbon-sulfur and car-bonchlorine bonds by the electrophilic ruthenium frag-ment ~Ru(r|-C5Me5) +'. J. Chem. Soc, Dalton Trans.1895-1901.Scheldt, W. R. and H.Nasri. 1995. Synthesis and molecu-lar structures of the redox pair (octaethylporphinato) bis(pentamethylene sulfide) osmium(II)and (octaethylpor-phinato)bis(pentamethylene sulfide)osmium(III) hexa-fluorophosphate. Inorg. Chem. 34:2190-2193.Hydrogen atomic coordinates and isotropic thermalparameters (Table 4S), anisotropic displacement parameters(Table 5S), bond distances and angles (Table 6S), least-square planes (Table 7S), observed and calculated structurefactors (Table 8S, 35 pages) are available from the authorsupon request.Literature CitedAdams, R. D.and S. B. Falloon. 1995. The chemistry ofthietane ligands in polynuclear metal carbonyl com-plexes. Chem. Rev. 95:2587-2598.Boorman, P. M.,N. L.Langdon, V.J. Mozol, M.Parvezand G. P. A. Yap. 1998. Syntheses, crystal structures,spectroscopic characterization, and electrochemicalstudies of the ditungsten(III) complexes Cl3W(u-L)3WC13 and [Cl3W(n-L)2(n-Cl)WCl3]- (L=l,4-dithi-ane, 1,4-thioxane, pms = pentamethylene sulfide). C-Sbond cleavage of the bridging thioether(s) in Cl3W(u-L)3WC13.Inorg. Chem. 37:6023-6029Journal of the Arkansas Academy of Science, Vol. 53, 1999149Journal of the Arkansas Academy of Science, Vol. 53 [1999], Art. 27Published by Arkansas Academy of Science, 1999

Synthesis and Molecular Structure of [CpRu(PPh\u3csub\u3e3\u3c/sub\u3e)(pms)\u3csub\u3e2\u3c/sub\u3e]OTf1.3/4 C\u3csub\u3e2\u3e\u3c/sub\u3eH\u3csub\u3e4\u3c/sub\u3eC1\u3csub\u3e2\u3c/sub\u3e

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Synthesis and Molecular Structure of [CpRu(PPh\u3csub\u3e3\u3c/sub\u3e)(pms)\u3csub\u3e2\u3c/sub\u3e]OTf1.3/4 C\u3csub\u3e2\u3e\u3c/sub\u3eH\u3csub\u3e4\u3c/sub\u3eC1\u3csub\u3e2\u3c/sub\u3e

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