Organometallics 1993,12, 4678-4681
4678
Sulfido and Related Derivatives of (C
~ M ~ ~ ) R U ~ ~ " I ~
Eric J. Houser, Somanath Dev, Ann E. Ogilvy, Thomas B. Rauchfuss,' and Scott R. Wilson School of Chemical Sciences, University of Illinois, 505 South Mathews Avenue, Urbana, Illinois 61801 Received March 8, 1 9 9 P Summary: The synthesis and properties of ( C N e ~ ) & u z Cl,Sy ( x , y: 2,4; 4 , 2 ) and (Cd4e&RupEq (E = S, Se, T e ) are described along with an improvedpreparation of (C5Me&&&. Single-crystal X-ray diffraction revealed the cubane structure of (C&fe5)&4Sed, which features two bonding Ru-Ru contacts.
Introduction
The Ru-S bonds to the persulfide average 2.220 A, and the S-S bond is quite short a t 1.991 A.6
This paper describes studies leading to the simple (pentamethylcyclopentadieny1)ruthenium sulfides [(C5Results and Discussion Me&RuIySz. The only reported member of this series is ( C S M ~ S ) ~ R UThis ~ S intensely ~.~ blue species is of interest (CaMea)zRuzSXl, The reaction of (RCsMe4)2RuzC4 because of the dynamic properties of the persulfido groups with 2 equiv of sulfurgave brown microcrystalline products and its desulfurization-induced reactivity. Further dethat were analyzed as (RCsMe4)2RuzC4Sz in good yields velopments in this area have been hampered by the (R = Me, Et; eq 1). The 'H NMR spectrum for (C5Me4inefficiency of the synthesis of this diruthenium species. The ready availability of (CsMe&Ru&L and (C5Me5)4(RC5Me4)2Ru2C14 + 1/4S8 (RCsMe4)2Ru2C14Sz(1) Ru&14 suggested a new approach to this p r ~ b l e m . ~ a Sulfur derivatives of (C5Mes)Ru have proven quite Et)zRuzC&Sz shows eight methyl singlets, indicating popular recently. The dinuclear compounds (CsMe5)zinequivalent C5Me4Et rings attached to a chiral dimetal Ruz(pSR)2 form in the exchange reaction of (CsMes)2center. The nonequivalence of the Ru sites is supported Ruz(p-OMe)z with thiols? The solid-state structure of by the lH NMR data for ( C ~ M ~ S ) ~ R U ~ Cwhich L & , shows the p-SEt derivative showed a puckered RuzS2 ring with two equally intense singlets. A structure consistent with Ru-S distances in the range 2.313-2.332(1) A and a Ruthe 'H NMR data for both compounds is Ru distance of 3.0754(5) A. The reactions of (C5Me& RuzC4 with thiol reagents give (C~Mes)zRuz(p-SR)3~/+ or ( C S M ~ S ) ~ R U Z C ~ ~depending ( ~ - S R ) ~ on , the conditions and the thioLS Structural studies on [ ( C S M ~ S ) ~ R U ~ ( ~ - S P ~ ) ~ I C ~ and (CsMes)2Ru2(p-SiPr)3 revealed quite different RuRu distances of 2.630(1) and 2.968(2) A, respectively, indicating that the Ru"' state is stabilized by Ru-Ru bonding. Treatment of (C5Mes)2Ru2C12(p-SiPr)2 with Since the Ru"' compound ( C S M ~ S ) ~ RisUreactive ~C~ (NH4)2MS4 (M = Mo, W) gives ( C S M ~ S ) ~ R U Z ( ~ - S ~ ) ( ~ - S ~ toward Sa, it seemed likely that the RulI species ( C S M ~ S ) ~ Pr)2? which is structurally rather reminscent of (C5R5)2RmC4 should also be oxidized by Sa. This was confirmed Ru&. This transformation illustrates the extrusion of by treatment of (CSMe&Ru&k with excess Sa,giving ((25532% from tetrachalc~genometalates,~ which may proceed Me&Ru2C12S4 in high yield (eq 2). (CsMe&Ru&l2S4 is with elimination of the polymeric MS2. The now prevalent Ru2(p-++Sz) function is also formed in the reaction of (CsMe5)4Ru4C1,+ Sa 2(CSMe5),Ru2C1,S4 (2) (NH4)2WS4 with (C6Me5)2Ru2CL1which gives the dark green cluster ( C S M ~ ~ ) ~ R U ~ ( ~ - S ~ ) ( ~ ~ - S ) ( ~ L - S ) ~ W S : ~ soluble in common organic solvents and very soluble in CH2C12 to give red-brown solutions. Its lH NMR spectrum * Abstract published in Advance ACS Abstracts, September 15,1993. (1) Rauchfuss, T. B.; Rodgers, D. P. S.; Wilson, S. R. J. Am. Chem. indicates equivalent ruthenium centers, and field desSOC.1986,108,3114. orption mass spectroscopy supports the proposed molec(2) Oshima, N.; Suzuki, H.; Moro-Oka, Y. Chem. Lett. 1984, 1161. ( 3 )Fagan, P. J.; Mahoney, W. S.; Calabrese, J. C.; Williams, I. D. ular formula. The IR spectrum of ( C ~ M ~ S ) ~ R Ushows ~C~ZS~ Organometallics 1990, 9, 1843. a medium-strength band a t 562 cm-l, which may be (4) Koelle, U.;Rietmann, C.; Englert, U.J. Organomet. Chem. 1992, attributed to vs.~;however the parent (CsMes)4R~C4 also 423, C20. (5) Hidai, M.; Imagawa, K.; Cheng, G.; Mizabe, Y.; Wakatsuki, Y.; shows bands a t 582 and 459 cm-l. The proposed structure Yamazaki, H. Chem. Lett. 1986,1299. Dev, S.; Imagawa, K.; Mizobe, Y.; is similar to that previously found for [(MeCsH4)2Cheng, G.; Wakatsuki,Y.;Yamazaki, H.; Hidai, M. Organometallics 1989, 8, 1232. Dev, S.; Mizobe, Y.; Hidai, M. Znorg. Chem. 1990,29,4797. Ruz(PPh3)2Se412+:8
-
-
(6) Mizobe, Y.; Hoaomizu,M.; Kawabata, J.; Hidai, M. J. Chem. Soc., Chem. Commun. 1991, 1226. ( 7 ) Ansari, M.; Chau, C. N.; Ibers, J. A.; Mahler, C. H. Inorg. Chem. 1989,2%, 650.
(8)Amarasekara, J.; Houser, E. J.; Rauchfuss, T. B.; Stern, C. L. Inorg. Chem. 1992,31, 1614.
0276-733319312312-4678$04.00/0 0 1993 American Chemical Society
Organometallics, Vol. 12, No. 11, 1993 4679
Notes
L
-1
The new compounds were tested as precursors to (C5Me5)2Ru,S4. Preliminary studies showed that Na reduction of (C5Me5)2Ru2Cl&& gave some of the desired product. A more efficientroute to (CjMe&Ru& involvestreatment of (C5Me&Ru&14& with (Me3Si)aS. The intensely blue product, obtained in 35% yield, was identified by its lH NMR spectrum as well as its reactivity (eq 3).9
CubaneClusters. The permethylated cubane clusters (C5Me5)4R~E4(E = S, Se, Te) were prepared from the reaction of (C5Me5)4Ru&14 with NaSH, (Me4N)SeH, and (Ph4P)TeH, respectively (eq 4). The formation of hy-
+
(C5Me5)4Ru4C14 4EH-
-
+ + 4C1-
2(C5Me5),Ru4E4 H,
Figure 1. View of (C5Me5)4Ru4Se4down the 2-fold axis. Table I. Principal Bond Distances (A) and Angles (deg) for (MeC&14),,R@4 (E = S, Te) and (C~Me5)4Ru,&e~~
Ru-Rub RwRuC Ru-Cp(centroid) Ru-Eb Ru-EC E...EC E...@) Ru-E-Ru~ Ru-E-Ru~ E-Ru-Eb E-Ru-E‘
2.76 3.60 1.87 2.3 1 2.37 2.96 3.45 73.3 100.9 96.4 77.8
2.89 4.02 1.88 2.59 2.65 3.27 3.92 67.9 100.5 98.7 77.4
2.96 3.76 1.811 2.43 2.49 3.14 3.63 75.1 99.6 96.5 79.4
These are average distances; esd’s are
