Welcome to LookChem.com Sign In|Join Free

Article Doi

Synthesis and study of ruthenium silylene complexes of the type [(η5-C5Me5)(Me3P) 2Ru=SiX2]+ (X = thiolate, Me, and Ph)

DOI: 10.1021/om980506e

Source and publish data:

Organometallics p. 5607 - 5619 (1998)

Update date:2022-07-29

Topics:

Authors:

Grumbine, Steven K.Grumbine, Steven K.

Mitchell, Gregory P.Mitchell, Gregory P.

Straus, Daniel A.Straus, Daniel A.

Don TilleyDon Tilley

Rheingold, Arnold L.Rheingold, Arnold L.

Read Full Text PDF DownLoad Join now for total 90,000,000 free articles

Article abstract of DOI:10.1021/om980506e

Various ruthenium silyl complexes of the type Cp*(Me3P)2RuSiR3 (Cp* = η5-C5Me5; SiR3 = SiCl3 (1), Si(NMe2)3 (2), Si(SEt)3 (3), Si(S-2-Naph)3 (4), Si[S(CH2)3S]Ph (5), Si(SCy)2Cl (6), and Si(SMes)2Cl (7, Mes = 2,4,6-trimethylphenyl)) were prepared by the reaction of Cp*(Me3P)2RuCH2SiMe3 with the appropriate silane HSiR3. Compound 3 was converted to the trifiate Cp*(Me3P)2RuSi(SEt)2OTf (8) by the reaction of 3 with Me3SiOTf. Similar reactions produced Cp*(Me3P)2RuSi(NMe2)2OTf (13), Cp*(Me3P)2RuSi(NMe2)(OTf)2 (14), Cp*(Me3P)2RuSi(SMes)2OTf (18), and Cp*(Me3P)2RuSi(SMes)(Cl)OTf (19). By NMR spectroscopy, compound 8 in dichloromethane solution appears to possess a labile trifiate group. Reactions of the triflates 8 and Cp*(Me3P)2RuSi(S-p-Tol)2OTf (10) with NaBPh4 provided the silylene complexes [Cp*(Me3P)2RuSi(SR)2][BPh4] (20, R = Et; 21, R = p-Tol). Similarly, the reaction of 6 with NaBPh4 gave [Cp*(Me3P)2RuSi(SCy)2][BPh4] (22), and the reaction of 4 with B(C6F5)3 produced [Cp*(Me3P)2RuSi(S-2-Naph)2][MeB(C 6F5)3] (23). Silylene complexes 20-23 display characteristic 29Si NMR shifts in the region of δ 250-270. The non-heteroatom-stabilized silylene complexes [Cp*(Me3P)2RuSiR2][B(C6F 5)4] (24, R = Me; 25, R = Ph), obtained via reactions of (Et2O)LiB(C6F5)4 with Cp*(Me3P)2RuSiR2OTf (11, R = Me; 12, R = Ph) exhibit 29Si NMR shifts around δ 300. The crystal structure of 24 revealed a Ru-Si distance of 2.238(2) A, and the Cp*(centroid)-Ru-Si-Me dihedral angle is 34°. Compound 24 reacts quantitatively with 1 equiv of PMe3 or PPh3 in dichloromethane-d2 to form the base-stabilized silylene complexes [Cp*(Me3P)2RuSiMe2(PR 3)][B(C6F5)4] (28, R = Me; 29, R = Ph), identified by 1H and 31P NMR spectroscopy. These complexes are thermally labile and decompose with elimination of the dimethylsilylene fragment to give [Cp*(Me3P)2RuPR3][B(C6F 5)4] (R = Me, Ph). The ylide CH2PPh3 reacts with 24 to form [Cp*(Me3P)2RuSiMe2CH2PPh 3][B(C6F5)4] (32a), and the characterization of [Cp*(Me3P)2RuSiMe2CH2PPh 3][OTf] (32b) by X-ray crystallography suggests that the complex is best viewed as a ruthenium silyl derivative with the positive charge localized on the ylide phosphorus atom. Reactions of 20 and 24 with hydrogen proceed slowly and result in relatively complex product mixtures that contain various ruthenium hydride species. The reaction involving 20 also produced HSi(SEt)3, perhaps via redistribution of initially formed H2Si(SEt)2. For the reaction of 24 with hydrogen, no H2SiMe2 was detected in the product mixture. The reaction of 20 with H3SiSiPh3 gave [Cp*(Me3P)2Ru(H)(SiH2SiPh 3)][BPh4] (35) and HSi(SEt)3, and the corresponding reaction of H3SiMes in dichloromethane gave [Cp*(Me3P)2RuHCl][BPh4] (34), BPh3, and H2SiMes(SEt), among other products. By NMR spectroscopy, the intermediate [Cp*(Me3P)2Ru(H)(SiH2Mes)][BPh 4] (36) was observed for the latter process. Compound 36, generated independently by reaction of [Cp*(Me3P)2Ru(NCMe)][BPh4] with H3SiMes, was shown to react with HSi(SEt)3 to give H2SiMes(SEt).

View More

Full text of DOI:10.1021/om980506e

Organometallics 1998, 17, 5607-5619  
5607  
Syn th esis a n d Stu d y of Ru th en iu m Silylen e Com p lexes  
of th e Typ e [(η5-C5Me5)(Me3P )2Ru dSiX2]+ (X ) Th iola te,  
Me, a n d P h )  
Steven K. Grumbine, Gregory P. Mitchell, Daniel A. Straus,† and T. Don Tilley*  
Department of Chemistry, University of California at Berkeley,  
Berkeley, California 94720-1460  
Arnold L. Rheingold*  
Department of Chemistry, University of Delaware, Newark, Delaware 19716  
Received J une 18, 1998  
Various ruthenium silyl complexes of the type Cp*(Me3P)2RuSiR3 (Cp* ) η5-C5Me5; SiR3  
) SiCl3 (1), Si(NMe2)3 (2), Si(SEt)3 (3), Si(S-2-Naph)3 (4), Si[S(CH2)3S]Ph (5), Si(SCy)2Cl (6),  
and Si(SMes)2Cl (7, Mes ) 2,4,6-trimethylphenyl)) were prepared by the reaction of Cp*-  
(Me3P)2RuCH2SiMe3 with the appropriate silane HSiR3. Compound 3 was converted to the  
triflate Cp*(Me3P)2RuSi(SEt)2OTf (8) by the reaction of 3 with Me3SiOTf. Similar reactions  
produced Cp*(Me3P)2RuSi(NMe2)2OTf (13), Cp*(Me3P)2RuSi(NMe2)(OTf)2 (14), Cp*(Me3P)2-  
RuSi(SMes)2OTf (18), and Cp*(Me3P)2RuSi(SMes)(Cl)OTf (19). By NMR spectroscopy,  
compound 8 in dichloromethane solution appears to possess a labile triflate group. Reactions  
of the triflates 8 and Cp*(Me3P)2RuSi(S-p-Tol)2OTf (10) with NaBPh4 provided the silylene  
complexes [Cp*(Me3P)2RuSi(SR)2][BPh4] (20, R ) Et; 21, R ) p-Tol). Similarly, the reaction  
of 6 with NaBPh4 gave [Cp*(Me3P)2RuSi(SCy)2][BPh4] (22), and the reaction of 4 with B(C6F5)3  
produced [Cp*(Me3P)2RuSi(S-2-Naph)2][MeB(C6F5)3] (23). Silylene complexes 20-23 display  
characteristic 29Si NMR shifts in the region of δ 250-270. The non-heteroatom-stabilized  
silylene complexes [Cp*(Me3P)2RuSiR2][B(C6F5)4] (24, R ) Me; 25, R ) Ph), obtained via  
reactions of (Et2O)LiB(C6F5)4 with Cp*(Me3P)2RuSiR2OTf (11, R ) Me; 12, R ) Ph) exhibit  
29Si NMR shifts around δ 300. The crystal structure of 24 revealed a Ru-Si distance of  
2.238(2) Å, and the Cp*(centroid)-Ru-Si-Me dihedral angle is 34°. Compound 24 reacts  
quantitatively with 1 equiv of PMe3 or PPh3 in dichloromethane-d2 to form the base-stabilized  
silylene complexes [Cp*(Me3P)2RuSiMe2(PR3)][B(C6F5)4] (28, R ) Me; 29, R ) Ph), identified  
1
by H and 31P NMR spectroscopy. These complexes are thermally labile and decompose  
with elimination of the dimethylsilylene fragment to give [Cp*(Me3P)2RuPR3][B(C6F5)4] (R  
) Me, Ph). The ylide CH2PPh3 reacts with 24 to form [Cp*(Me3P)2RuSiMe2CH2PPh3]-  
[B(C6F5)4] (32a ), and the characterization of [Cp*(Me3P)2RuSiMe2CH2PPh3][OTf] (32b) by  
X-ray crystallography suggests that the complex is best viewed as a ruthenium silyl derivative  
with the positive charge localized on the “ylide” phosphorus atom. Reactions of 20 and 24  
with hydrogen proceed slowly and result in relatively complex product mixtures that contain  
various ruthenium hydride species. The reaction involving 20 also produced HSi(SEt)3,  
perhaps via redistribution of initially formed H2Si(SEt)2. For the reaction of 24 with  
hydrogen, no H2SiMe2 was detected in the product mixture. The reaction of 20 with H3-  
SiSiPh3 gave [Cp*(Me3P)2Ru(H)(SiH2SiPh3)][BPh4] (35) and HSi(SEt)3, and the corresponding  
reaction of H3SiMes in dichloromethane gave [Cp*(Me3P)2RuHCl][BPh4] (34), BPh3, and H2-  
SiMes(SEt), among other products. By NMR spectroscopy, the intermediate [Cp*(Me3P)2-  
Ru(H)(SiH2Mes)][BPh4] (36) was observed for the latter process. Compound 36, generated  
independently by reaction of [Cp*(Me3P)2Ru(NCMe)][BPh4] with H3SiMes, was shown to  
react with HSi(SEt)3 to give H2SiMes(SEt).  
In tr od u ction  
attention is largely derived from the possibility that  
metal-silicon double bonds might participate in a wide  
range of organosilicon transformations.1-24 Several  
processes such as the dehydropolymerization of sil-  
anes,1c,11 the transfer of silylenes to unsaturated com-  
pounds,7b,c,8b,10,19 and the redistribution of substituents  
Transition metal-silylene complexes have been the  
focus of intense research interest in recent years.1 This  
† Current address: Chemistry Department, San J ose State Univer-  
sity, San J ose, CA 95192-0101.  
10.1021/om980506e CCC: $15.00 © 1998 American Chemical Society  
Publication on Web 11/14/1998  
5608 Organometallics, Vol. 17, No. 26, 1998  
Grumbine et al.  
at silicon1g,7a have been proposed to involve silylene  
intermediates. Considerable effort has therefore been  
devoted to the verification of these proposals, and  
consequently dramatic advances in transition metal-  
silylene chemistry have been made in recent years. In  
1987, the synthesis and characterization of donor-  
stabilized silylene complexes were reported,5a,20a and in  
1990 base-free silylene complexes of the type [Cp*-  
(Me3P)2RudSi(SR)2]BPh4 (Cp* ) η5-C5Me5) were com-  
municated.22a Since then, several more complexes with  
bonds between a transition metal and sp2 silicon have  
been isolated,22,23 and initial reactivity studies on such  
compounds have been carried out.24  
(1) (a) Tilley, T. D. In The Silicon-Heteroatom Bond; Patai, S.,  
Rappoport, Z., Eds.; Wiley: New York, 1991; Chapters 9 and 10, pp  
245 and 309. (b) Tilley, T. D. In The Chemistry of Organic Silicon  
Compounds; Patai, S., Rappoport, Z., Eds.; Wiley: New York, 1989;  
Chapter 24, p 1415. (c) Tilley, T. D. Comments Inorg. Chem. 1990, 10,  
37. (d) Lickiss, P. D. Chem. Soc. Rev. 1992, 271. (e) Pannell, K. H.;  
Sharma, H. K. Chem. Rev. 1995, 95, 1351. (f) Zybill, C. Top. Curr.  
Chem. 1991, 160, 1. (g) Curtis, M. D.; Epstein, P. S. Adv. Organomet.  
Chem. 1981, 19, 213.  
(2) (a) Pannell, K. H.; Cervantes, J .; Hernandez, C.; Cassias, J .;  
Vincenti, S. Organometallics 1986, 5, 1056. (b) Pannell, K. H.; Rozell,  
J . M, J r.; Hernandez, C. J . Am. Chem. Soc. 1989, 111, 4482. (c) Pannell,  
K. H.; Wang, L.-J .; Rozell, J . M. Organometallics 1989, 8, 550. (d)  
Pannell, K. H.; Sharma, H. Organometallics 1991, 10, 954. (e) J ones,  
K. L.; Pannell, K. H. J . Am. Chem. Soc. 1993, 115, 11336. (f)  
Hernandez, C.; Sharma, H. K.; Pannell, K. H. J . Organomet. Chem.  
1993, 462, 259. (g) Pannell, K. H.; Brun, M.-C.; Sharma, H.; J ones,  
K.; Sharma, S. Organometallics 1994, 13, 1075. (h) Pannell, K. H.;  
Sharma, H. K.; Kapoor, R. N.; Cervantes Lee, F. J . Am. Chem. Soc.  
1997, 119, 9315. (i) Zhang, Z. Y.; Sanchez, R.; Pannell, K. H.  
Organometallics 1995, 14, 2605.  
(3) (a) Tobita, H.; Ueno, K.; Ogino, H. Bull. Chem. Soc. J pn. 1988,  
61, 2797. (b) Ueno, K.; Tobita, H.; Shimoi, M.; Ogino, H. J . Am. Chem.  
Soc. 1988, 110, 4092. (c) Ueno, K.; Tobita, H.; Ogino, H. Chem. Lett.  
1990, 369. (d) Ueno, K.; Kakano, K.; Ogino, H. Chem. Lett. 1996, 459.  
(e) Okazaki, M.; Tobita, H.; Ogino, H. J . Chem. Soc., Dalton Trans.  
1997, 3531. (f) Tobita, H.; Ueno, K.; Shimoi, M.; Ogino, H. J . Am. Chem.  
Soc. 1990, 112, 3415. (g) Takeuchi, T.; Tobita, H.; Ogino, H. Organo-  
metallics 1991, 10, 835. (h) Koe, J .; Tobita, H.; Ogino, H. Organome-  
tallics 1992, 11, 2479. (i) Ueno, K.; Tobita, H.; Ogino, H. J . Organomet.  
Chem. 1992, 430, 93. (j) Ueno, K.; Tobita, H.; Seki, S.; Ogino, H. Chem.  
Lett. 1993, 1723. (k) Kobayashi, H.; Ueno, K.; Ogino, H. Organome-  
tallics 1995, 14, 5490. (l) Ueno, K.; Masuko, A.; Ogino, H. Organome-  
tallics 1997, 16, 5023.  
(4) Haynes, A.; George, M. W.; Haward, M. T.; Poliakoff, M.; Turner,  
J . J .; Boag, N. M.; Green, M. J . Am. Chem. Soc. 1991, 113, 2011.  
(5) (a) Zybill, C.; Mu¨ller, G. Angew. Chem., Int. Ed. Engl. 1987, 26,  
669. (b) Zybill, C.; Wilkinson, D. L.; Mu¨ller, G. Angew. Chem., Int. Ed.  
Engl. 1988, 27, 583. (c) Zybill, C.; Mu¨ller, G. Organometallics 1988, 7,  
1368. (d) Zybill, C.; Wilkinson, D. L.; Leis, C.; Mu¨ller, G. Angew. Chem.,  
Int. Ed. Engl. 1989, 28, 203. (e) Leis, C.; Zybill, C.; Lachmann, J .;  
Mu¨ller, G. Polyhedron 1991, 10, 1163. (f) Handwerker, H.; Paul, M.;  
Riede, J .; Zybill, C. J . Organomet. Chem. 1993, 459, 151. (g) Hand-  
werker, H.; Paul, M.; Blumel, J .; Zybill, C. Angew. Chem., Int. Ed. Engl.  
1993, 32, 1313. (h) Handwerker, H.; Leis, C.; Gamper, S.; Zybill, C.  
Inorg. Chim. Acta 1992, 200, 763.  
In general, silylene complexes are much more difficult  
to prepare than the analogous carbene compounds,  
which are often obtained from unsaturated starting  
materials (e.g., CO or N2CR2) that do not have stable  
silicon analogues or by use of an electrophilic reagent  
to abstract a substituent (e.g., hydride, methoxide, or  
halide) from an alkyl complex.25 Early attempts to  
apply the latter method to transition metal-silicon  
compounds were unsuccessful, because the extreme  
Lewis acidity of the resulting silylene ligand can give  
rise to secondary reactions (such as halide ion transfer)  
which form new bonds to silicon.26 Nonetheless we have  
developed methods for the synthesis of cationic silylene  
complexes, based on abstraction of a group bound to  
silicon. This approach has focused on electron-rich  
metal fragments (e.g., Cp*(Me3P)2Ru) expected to sta-  
bilize an electron-deficient silicon center. In addition,  
this method requires use of “noncoordinating” anions  
-
such as BPh4 and B(C6F5)4-, which exhibit low reac-  
tivities toward the resulting three-coordinate silicon  
centers. Here we report investigations into the synthe-  
sis, characterization, and reactivity of cationic ruthe-  
nium silylene complexes of the type [Cp*(Me3P)2Rud  
SiX2]+.  
(20) (a) Straus, D. A.; Tilley, T. D.; Rheingold, A. L.; Geib, S. J . J .  
Am. Chem. Soc. 1987, 109, 5872. (b) Straus, D.; Zhang, C.; Quimbita,  
G. E.; Grumbine, S. D.; Heyn, R. H.; Tilley, T. D.; Rheingold, A. L.;  
Geib, S. J . J . Am. Chem. Soc. 1990, 112, 2673. (c) Grumbine, S. K.;  
Straus, D. A.; Tilley, T. D.; Rheingold, A. L. Polyhedron 1995, 14,  
127.  
(21) (a) Heyn, R. H.; Tilley, T. D. J . Am. Chem. Soc. 1992, 114, 1917.  
(b) Mitchell, G. P.; Tilley, T. D.; Yap, G. P. A.; Rheingold, A. L.  
Organometallics 1995, 14, 5472. (c) Mitchell, G. P.; Tilley, T. D.  
Organometallics 1996, 15, 3477. (d) Mitchell, G. P.; Tilley, T. D.  
Organometallics 1998, 17, 2912. (e) Mitchell, G. P.; Tilley, T. D. J . Am.  
Chem. Soc. 1998, 120, 7635.  
(22) (a) Straus, D. A.; Grumbine, S. D.; Tilley, T. D. J . Am. Chem.  
Soc. 1990, 112, 7801. (b) Grumbine, S. D.; Tilley, T. D.; Rheingold, A.  
L. J . Am. Chem. Soc. 1993, 115, 358. (c) Grumbine, S. D.; Tilley, T.  
D.; Rheingold, A. L.; Arnold, F. P. J . Am. Chem. Soc. 1993, 115, 7884.  
(d) Grumbine, S. K.; Tilley, T. D.; Arnold, F. P.; Rheingold, A. L. J .  
Am. Chem. Soc. 1994, 116, 5495. (e) Mitchell, G. P.; Tilley, T. D. Angew.  
Chem., Int. Ed. 1998, 37, 2524. (f) Feldman, J .; Mitchell, G. P.; Nolte,  
J .-P.; Tilley, T. D. J . Am. Chem. Soc. 1998, 120, 11184.  
(23) Denk, M.; Hayashi, R. K.; West, R. J . Chem. Soc., Chem.  
Commun. 1994, 33.  
(6) Pestana, D. C.; Koloski, T. S.; Berry, D. H. Organometallics 1994,  
13, 4173.  
(7) (a) Kobayashi, T.; Hayahi, T.; Yamashita, H.; Tanaka, M. Chem.  
Lett. 1988, 1411. (b) Yamashita, H.; Tanaka, M.; Goto, M. Organome-  
tallics 1992, 11, 3227. (c) Tanaka, Y.; Yamashita, H.; Tanaka, M.  
Organometallics 1995, 14, 530. (d) Sakakura, T.; Kumberger, O.; Tan,  
R. P.; Arthur, M.-P.; Tanaka, M. J . Chem. Soc., Chem. Commun. 1995,  
193.  
(8) (a) Yamamoto, K.; Okinoshima, H.; Kumada, M. J . Organomet.  
Chem. 1970, 23, C7. (b) Yamamoto, K.; Okinoshima, H.; Kumada, M.  
J . Organomet. Chem. 1971, 27, C31. (c) Okinoshima, H.; Yamamoto,  
K.; Kumada, M. J . Am. Chem. Soc. 1972, 94, 9263.  
(9) Tamao, K.; Sun, G.-R.; Kawachi, A. J . Am. Chem. Soc. 1995, 117,  
8043.  
(10) Seyferth, D.; Shannon, M. L.; Vick, S. C.; Lim, T. F. O.  
Organometallics 1985, 4, 57.  
(11) Brown-Wensley, K. A. Organometallics 1987, 6, 1590.  
(12) Sakurai, H.; Kamiyama, Y.; Nakadaira, Y. J . Am. Chem. Soc.  
1977, 99, 3879.  
(13) Chang, L. S.; J ohnson, M. P.; Fink, M. J . Organometallics 1989,  
8, 1369.  
(14) (a) Corriu, R.; Lanneau, G. F.; Priou, C. Angew. Chem., Int. Ed.  
Engl. 1991, 9, 1130. (b) Corriu, R. J .; Lanneau, G. F.; Chauhan, P. S.  
Organometallics 1993, 12, 2001. (c) Corriu, R. J . P.; Chauhan, B. P.  
S.; Lanneau, G. F. Organometallics 1995, 14, 1646.  
(15) Auner, N.; Wagner, C.; Herdtweck, E.; Heckel, M.; Hiller, W.  
Bull. Soc. Chim. Fr. 1995, 132, 599.  
(16) (a) Braunstein, P.; Stern, C.; Strohmann, C.; Tong, N. Chem.  
Commun. 1996, 2237. (b) Braunstein, P.; Huch, V.; Stern, C.; Veith,  
M. Chem. Commun. 1996, 2041.  
(24) (a) Mitchell, G. P.; Tilley, T. D. J . Am. Chem. Soc. 1997, 119,  
11236. (b) Grumbine, S. K.; Tilley, T. D. J . Am. Chem. Soc. 1994, 116,  
6951.  
(25) (a) Fischer, E. O. Adv. Organomet. Chem. 1976, 14, 1. (b)  
Cardin, D. J .; Cetinkaya, B.; Lappert, M. F. Chem. Rev. 1972, 72, 545.  
(c) Casey, C. P. In Reactive Intermediates; J ones, M., J r., Moss, R. A.,  
Eds.; Wiley: New York, 1981; Vol. II, p 135. (d) Kegley, S. E.;  
Brookhart, M.; Husk, G. R. Organometallics 1982, 1, 760. (e) Tam.,  
W.; Lin, G.-Y.; Wong, W.-K.; Kiel, W. A.; Wong, V. K.; Gladysz, J . A.  
J . Am. Chem. Soc. 1982, 104, 141. (f) Yu, Y. S.; Angelici, R. J .  
Organometallics 1983, 2, 1018. (g) Barefield, E. K.; McCarten, P.;  
Hillhouse, M. C. Organometallics 1985, 4, 1682. (h) J olly, P. W.; Pettit,  
R. J . Am. Chem. Soc. 1966, 88, 5044. (i) Hoskins, S. V.; Rickard, C. E.  
F.; Roper, W. R. J . Chem. Soc., Chem. Commun. 1984, 1000. (j)  
Calabrese, J . C.; Roe, D. C.; Thorn, D. L.; Tulip, T. H. Organometallics  
1984, 3, 1223.  
(17) Nlate, S.; Herdtweck, E.; Fischer, R. A. Angew. Chem., Int. Ed.  
Engl. 1996, 35, 1861.  
(18) Clarke, M. P.; Davidson, I. M. T. J . Organomet. Chem. 1991,  
408, 149.  
(26) (a) Aylett, B. J . J . Organomet. Chem. Lib. 1980, 9, 327. (b)  
Marks, T. J .; Seyam, A. M. Inorg. Chem. 1974, 13, 1624. (c) Thum, G.;  
Malisch, W. J . Organomet. Chem. 1984, 264, C5. (d) Malisch, W. Chem.  
Ber. 1974, 107, 7, 3835. (e) Schmid, G.; Balk, H.-J . J . Organomet. Chem.  
1974, 80, 257.  
(19) Palmer, W. S.; Woerpel, K. A. Organometallics 1997, 16, 4824.  
Ruthenium Silylene Complexes  
Resu lts a n d Discu ssion  
Organometallics, Vol. 17, No. 26, 1998 5609  
(SEt)2][OTf], as evidenced by NMR spectroscopy. In  
dichloromethane-d2 the inequivalent methylene protons  
of the SEt groups exchange rapidly, appearing as a  
Syn th esis of P r ecu r sor Ru th en iu m Silyl Com -  
p lexes. We have previously described a general method  
for preparing ruthenium silyl complexes of the type Cp*-  
(Me3P)2RuSiR3,20b which involves reaction of the ruthe-  
nium alkyl complex Cp*(Me3P)2RuCH2SiMe327 with the  
appropriate silane in hot toluene. As shown in eq 1,  
this procedure was useful for the preparation of silyl  
complexes 1-7 (2-Naph ) 2-naphthyl; Cy ) cyclohexyl;  
Mes ) mesityl). These light yellow silyl complexes are  
only somewhat air-sensitive, except for 2 and 5, which  
decompose within 2 h when exposed to air. Attempts  
to form silyl complexes by reaction of Cp*(Me3P)2RuCH2-  
SiMe3 with the sterically demanding silanes HSi-  
(SMes)3, HSi(SCy)3, HSi[S(2,4,6-iPr3C6H2)]3, and HSi-  
(NPh2)2Cl in toluene were unsuccessful and instead gave  
the C-H activation products Cp*(Me3P)2Ru(m-Tol) and  
Cp*(Me3P)2Ru(p-Tol).28  
1
single H NMR resonance (q, δ 2.88) down to -70 °C.  
However in the less polar solvent toluene-d8, the process  
that exchanges these protons is slowed considerably,  
resulting in an observed coalescence temperature of 21  
°C (∆Gq ) 14.9 ( 0.3 kcal mol-1). These results are  
most consistent with an exchange mechanism involving  
dissociation of triflate anion to form the silylene com-  
plex, followed by return of the triflate anion to the  
opposite face of the silylene ligand (possibly assisted by  
rapid rotation about the Ru-Si bond). A similar  
exchange process has been observed for Cp(NO)-  
(Ph3P)ReGePh2OTf.30  
Attempts to convert the tri(amino)silyl complex 2 to  
the triflate Cp*(Me3P)2RuSi(NMe2)2OTf (13) were com-  
plicated by the competing reaction of 13 with Me3SiOTf  
to produce Cp*(Me3P)2RuSi(NMe2)(OTf)2 (14). A sample  
of pure 13 was obtained in 17% yield from the 1:1  
reaction of 2 with Me3SiOTf, and 14 was isolated with  
use of excess Me3SiOTf reagent. For comparison, the  
triflate Cp*(Me3P)2RuSi(S-p-Tol)2OTf (10), which may  
be isolated cleanly from the reaction of Cp*(Me3P)2RuSi-  
(S-p-Tol)3 with Me3SiOTf, is also readily converted to  
the bis(triflate) Cp*(Me3P)2RuSi(S-p-Tol)(OTf)2 (15).20c  
The latter complex has proven to be a valuable precur-  
sor to complexes possessing the Si(S-p-Tol) “silylyne”  
fragment22b,31 and may also be used to prepare silyl  
complexes with chelating dithiolate groups, as shown  
in eq 3. Unfortunately, attempts to convert complexes  
Our synthetic route to cationic silylene complexes  
employs labile triflato(silyl) derivatives of the type Cp*-  
(Me3P)2RuSiR2OTf (OTf ) OSO2CF3), which are con-  
verted to the silylene complexes via exchange of triflate  
for a less-coordinating anion. These triflate derivatives  
are generally obtained by the abstraction of a group  
bound to silicon with trimethylsilyl triflate, as il-  
lustrated by the synthesis of 8 (eq 2). Complex 8 is  
similar to the previously reported ruthenium complexes  
Cp*(Me3P)2RuSiR2OTf (9, R ) Cl; 10, R ) S-p-Tol; 11,  
R ) Me; 12, R ) Ph),20b,c which possess covalently bound  
triflate groups as determined by X-ray crystallography  
and infrared spectroscopy29 (ν(SO3) vibrational modes  
corresponding to covalently bound triflates were ob-  
served at ca. 1360 cm-1). These triflates are chemically  
labile and can be displaced by a donor such as acetoni-  
trile to give base-stabilized silylene complexes of the  
type [Cp*(Me3P)2RuSiR2(NCMe)][OTf].20b,c In acetoni-  
trile, triflate is displaced from 8 to produce [Cp*(Me3P)2-  
RuSi(SEt)2(NCMe)][OTf], as indicated by an ν(SO3)  
infrared band for ionic triflate (1268 cm-1).29  
16 and 17 to triflato(silyl) complexes via reactions with  
trimethylsilyl triflate or triflic acid met with limited  
success. Although the expected triflates were obtained,  
they were contaminated by 10-20% of decomposition  
products, and attempts at further purification resulted  
in the accumulation of more impurities (presumably  
decomposition products).  
Reaction of Me3SiOTf with 7 produced two different  
complexes resulting from competitive abstraction of both  
chloride and thiolate (eq 4). In dichloromethane-d2, 18  
Me3SiOTf  
Cp*(Me3P)2RuSi(SEt)3  
8
-Me3SiSEt  
3
Cp*(Me3P)2RuSi(SEt)2OTf U  
8
[Cp*(Me3P)2RuSi(SEt)2][OTf] (2)  
The triflate complex 8 appears to be in equilibrium  
with the cationic silylene complex [Cp*(Me3P)2RudSi-  
(27) Tilley, T. D.; Grubbs, R. H.; Bercaw, J . E. Organometallics 1984,  
3, 274.  
(28) (a) Tilley, T. D.; Togni, A.; Paciello, R. A.; Bercaw, J . E.; Grubbs,  
R. H. Unpublished results. (b) Bryndza, H. E.; Domaille, P. J .; Paciello,  
R. A.; Bercaw, J . E. Organometallics 1989, 8, 379. (c) Lehmkuhl, H.;  
Bellenbaum, M.; Grundke, J .; Mauermann; H.; Kru¨ger, C. Chem. Ber.  
1988, 121, 1719.  
1
and 19 were observed to form in a 2:1 ratio (by H and  
31P NMR spectroscopy). When carried out on a pre-  
(30) Lee, K. E.; Gladysz, J . A. Polyhedron 1988, 7, 2209.  
(31) Grumbine, S. D.; Chadha, R. K.; Tilley, T. D. J . Am. Chem. Soc.  
1992, 114, 1518.  
(29) Lawrance, G. A. Chem. Rev. 1986, 86, 17.  
5610 Organometallics, Vol. 17, No. 26, 1998  
Ta ble 1. 29Si NMR Sh ift Da ta for Silylen e Com p lexes  
Grumbine et al.  
complex  
29Si NMR shift (ppm)  
[Cp*(Me3P)2RuSi(SEt)2][BPh4] (20)  
[Cp*(Me3P)2RuSi(S-p-Tol)2][BPh4] (21)  
[Cp*(Me3P)2RuSi(SCy)2][BPh4] (22)  
[Cp*(Me3P)2RuSi(S-2-Naph)2][B(C6F6)3(S-2-Naph)] (23)  
[Cp*(Me3P)2RuSiMe2][B(C6F5)4] (24)  
[Cp*(Me3P)2RuSiPh2][B(C6F5)4] (25)  
264.4 br  
2
259.4 (t, J SiP ) 34 Hz)  
2
268.67 (t, J SiP ) 35 Hz)  
2
260.51 (t, J SiP ) 33 Hz)  
311.41 br  
2
299 (t, J SiP ) 32 Hz)  
was observed at -60 °C. The J SiP coupling constants  
for these silylene complexes are similar to those ob-  
served for the precursor silyl complexes, but this is  
perhaps not surprising given the insensitivity of J CP  
coupling constants for related alkyl and cationic carbene  
complexes to changes in hybridization at carbon.34  
Since bridging silylene complexes are also known to  
exhibit downfield 29Si NMR shifts,1a,b it was important  
to establish the degrees of association for 20 and 21.  
The fact that the silicon atoms in these complexes are  
coupled to only two phosphorus nuclei rules out alterna-  
tive structures with bridging silylene ligands. In ad-  
dition, a molecular weight determination for 21 (isopi-  
estic method, dichloromethane) gave a value of 990 g  
mol-1, which is consistent with a tight ion pair in  
solution (calcd: 982). The ionic nature of 20 and 21 is  
also supported by solution conductivity measurements  
(see Experimental Section).  
parative scale, only 19 was isolated, in 49% yield. The  
inequivalent phosphorus atoms in 19 are observed in  
benzene-d6 as doublets in the 31P NMR spectrum, at  
0.52 and 2.06 ppm (J PP ) 39 Hz); however when the  
same spectrum was taken in dichloromethane-d2, one  
broad peak was observed at 2.03 ppm. This phosphorus-  
exchange process is probably due to the rapid and  
reversible dissociation of triflate in dichloromethane-  
d2, as observed for Cp*(Me3P)2RuSi(SEt)2OTf (8).  
Syn th esis a n d Ch a r a cter iza tion of Th iola te-  
Su bstitu ted Silylen e Com p lexes. The ruthenium  
silyls described in the previous section were examined  
as precursors to cationic silylene complexes. The syn-  
thetic strategy involved anion exchange, with introduc-  
tion of a less-coordinating anion. As shown in eq 5, the  
triflate derivatives 8 and 10 react with NaBPh4 in  
dichloromethane to produce the heteroatom-stabilized  
silylene complexes [Cp*(Me3P)2RuSi(SR)2][BPh4] (20, R  
) SEt; 21, R ) S-p-Tol), which were isolated as yellow,  
crystalline solids. Somewhat surprisingly, the chloride  
Numerous attempts to grow X-ray quality crystals of  
20-22 were unsuccessful. We therefore examined use  
-
of anions other than BPh4 as counteranions for the  
cationic silylene complexes. A suitable anion must be  
noncoordinating and inert toward the reactive, electro-  
philic silylene center.35 Some of the salts that produced  
reasonably stable silylene complexes (from 10, as de-  
termined by 1H and 31P NMR spectra) were NaB(p-Tol)4,  
NaB(3,5-Me2C6H3)4, LiB(C6F5)4, NaC2B9H12, and NaCo-  
(C2B9H12)2. Unfortunately, these variations of the anion  
did not produce X-ray quality crystals. Anions that  
-
produced mainly decomposition products included PF6  
,
-
ClO4-, Ph3BNCBPh3-, and B[3,5-(CF3)2C6H3]4  
.
A related synthetic approach involves use of a strong  
Lewis acid to abstract a group bound to silicon in a  
metal silyl complex. The feasibility of this method was  
demonstrated by the reaction in eq 6, which gives the  
group of 6 also participates in a salt-elimination reaction  
with NaBPh4, to give 22.  
Elemental analyses showed that these materials do  
not contain solvent which could be coordinated to the  
silylene silicon atom. Compounds 20-22 exhibit 29Si  
NMR resonances characteristic of silylene complexes,  
falling in the 250-270 ppm range (Table 1), significantly  
downfield of the resonances for ruthenium silyl com-  
plexes (-1 to 112 ppm).1a,b,20b This is to be expected on  
the basis of 29Si correlations to 13C NMR spectroscopy32  
since the 13C shifts in terminal carbene complexes are  
generally in the range 240-370 ppm. For example, the  
13C NMR shift for the carbene carbon in [Cp(CO)2Rud  
C(SMe)2][PF6] is 285.3 ppm.33 At 23 °C, compound 21  
exhibits a broad 29Si NMR resonance at 250.6 ppm,  
which sharpens to a well-defined triplet at -80 °C (δ  
259.4, J SiP ) 34 Hz). For 22, a broad peak at δ 264.4  
new silylene complex 23. The 29Si NMR chemical shift  
for 23 (260.5 ppm, t, J SiP ) 33 Hz; dichloromethane-d2  
solution) is characteristic for a silylene complex. This  
(34) (a) Brookhart, M.; Tucker, J . R.; Husk, G. R. J . Am. Chem. Soc.  
1983, 105, 258. (b) Kiel, W. A.; Lin, G.-Y.; Bodner, G. S.; Gladysz, J .  
A. J . Am. Chem. Soc. 1983, 105, 4958. (c) Patton, A. T.; Strouse, C. E.;  
Knobler, C. B.; Gladysz, J . A. J . Am. Chem. Soc. 1983, 105, 5804. (d)  
Kiel, W. A.; Buhro, W. E.; Gladysz, J . A. Organometallics 1984, 3, 879.  
(e) Bly, R. S.; Wu, R.; Bly, R. K. Organometallics 1990, 9, 936.  
(35) Strauss, S. H. Chem. Rev. 1993, 93, 927.  
(32) Olah, G. A.; Field, L. D. Organometallics 1982, 1, 1485.  
(33) Matachek, J . R.; Angelici, R. J . Inorg. Chem. 1986, 25, 2877.  
Ruthenium Silylene Complexes  
Organometallics, Vol. 17, No. 26, 1998 5611  
reaction seems to be reversible, since only the starting  
silyl complex 4 was isolated upon attempted crystal-  
lization of 23 from dichloromethane/di(n-butyl) ether.  
36  
In a similar manner, Ph3CBPh4 reacts with Cp*-  
(Me3P)2RuSi(S-p-Tol)3 in dichloromethane-d2 to give the  
1
silylene complex 21 and Ph3C(S-p-Tol) (by H, 31P, and  
29Si NMR spectroscopy). Attempts to form silylene  
complexes via abstraction of chloride from Cp*(Me3P)2-  
RuSi(SCy)2Cl (6) with the Lewis acids YCp3, AlCl3, and  
ZnCl2 were not successful. In addition, the reaction of  
6 with SbCl5 in dichloromethane-d2 slowly produced 1  
through a series of chlorination reactions.  
Attempts were made to prepare silylene complexes  
via reactions of NaBPh4 with the triflate complexes 9,  
11, 12, 13, 15, and 19. These reactions did not produce  
isolable silylene complexes and typically resulted in  
production of multiple products (by H and 31P NMR  
spectroscopy; dichloromethane-d2) over an 8-30 h pe-  
riod.  
1
F igu r e 1. ORTEP view of the cation in [Cp*(Me3P)2Rud  
SiMe2][B(C6F5)4] (24).  
Ta ble 2. Selected Bon d Dista n ces (Å) a n d An gles  
(d eg) for 24  
Syn th esis a n d Ch a r a cter iza tion of Non -Heter o-  
a tom -Sta bilized Silylen e Com p lexes. The base-free  
silylene complexes described above feature π-donation  
from sulfur, which is expected to significantly stabilize  
the electron-deficient silicon center.22c Initial attempts  
to obtain silylene complexes without heteroatom sub-  
stituents involved reactions of Cp*(Me3P)2RuSiR2OTf  
(11, R ) Me; 12, R ) Ph) with NaBPh4 in dichlo-  
romethane. These reactions produced complex mix-  
tures, presumably resulting from decompositions of the  
initially generated silylene complexes. Reasoning that  
these decompositions might result from reactions be-  
(a) Bond Distances  
Ru-P(1)  
Ru-P(2)  
Ru-Si  
Si-C(17)  
Si-C(18)  
2.290(3)  
2.293(3)  
2.238(3)  
1.721(16)  
1.826(12)  
Ru-C(1)  
Ru-C(2)  
Ru-C(3)  
Ru-C(4)  
Ru-C(5)  
2.277(10)  
2.288(10)  
2.263(10)  
2.271(10)  
2.275(10)  
(b) Bond Angles  
P(1)-Ru-P(2)  
P(1)-Ru-Si  
P(2)-Ru-Si  
Si-Ru-C(1)  
Si-Ru-C(3)  
Si-Ru-C(5)  
93.0(1)  
92.8(1)  
89.1(1)  
154.3(3)  
101.3(3)  
119.4(3)  
C(17)-Si-C(18)  
Ru-Si-C(17)  
Ru-Si-C(18)  
Si-Ru-C(2)  
99.7(8)  
133.5(7)  
125.5(5)  
135.5(3)  
93.6(3)  
Si-Ru-C(4)  
-
tween the silylene silicon center and the BPh4 anion,  
P(1)-Ru-C(1)  
98.9(2)  
-
we employed the more chemically inert anion B(C6F5)4  
,
which is available as a dichloromethane-soluble lithium  
salt.  
The reagent LiB(C6F5)4‚OEt2 reacts rapidly with  
11 and 12 in dichloromethane-d2 at -30 °C to quan-  
titatively form the silylene complexes [Cp*(Me3P)2-  
RudSiMe2][B(C6F5)4] (24) and [Cp*(Me3P)2RudSiPh2]-  
[B(C6F5)4] (25), respectively (eq 7; by NMR spectroscopy).  
1,2-dichlorobenzene solution of 11 at 23 °C, followed by  
slow addition of Bu2O (over ca. 5 min) until crystals  
n
37  
began to form. Further crystallization at room temper-  
ature occurred over ca. 0.5 h to afford 24 in 38% yield.  
The molecular structure of the cation in 24 (Figure 1)  
consists of a dimethylsilylene ligand that is planar at  
silicon (summation of bond angles ) 359(1)°) and  
coordinated to a Cp*(Me3P)2Ru+ fragment. The Ru-Si  
distance of 2.238(2) Å is the shortest yet reported and  
slightly shorter than the Ru-Si bond lengths in Cp*-  
(Me3P)2RuSi[S(p-Tol)]Os(CO)4, 2.286(2) Å,22b and Cp*-  
(Me3P)2RuSi[S(p-Tol)](phen)2+, 2.269(5) Å.31 The Cp*-  
(centroid)-Ru-Si-Me dihedral angle is 34°. This angle  
deviates from what might be expected on the basis of  
efficient π-overlap involving the frontier orbitals of a  
CpL2M+ fragment,22d,38 which is expected to result in a  
dihedral angle of 0°.39  
The formations of 24 and 25 are signaled by character-  
istic downfield 29Si NMR shifts, at δ 299 (t, J SiP ) 32  
Hz) and 311 (br), respectively. These silylene complexes  
are unstable at room temperature in dichloromethane  
and decompose with half-lives of 7 and 3 h, respectively.  
Upon cooling a concentrated dichloromethane solution  
of 25 to -78 °C, orange-red crystals formed which  
desolvated upon isolation to the formula [Cp*(Me3P)2-  
RudSiPh2][B(C6F5)4]‚0.1CH2Cl2 (by combustion analy-  
sis). As expected, both 24 and 25 react with acetonitrile  
to give the previously characterized adducts [Cp*-  
(Me3P)2RuSiR2(NCMe)]+ (R ) Me,20c Ph20a,b) (which  
display 29Si NMR shifts of δ 110 and 96, respectively).  
X-ray quality crystals of 24 were eventually obtained  
Th er m a l Decom p osition s of Silylen e Com p lexes.  
Thiolate-substituted silylene complexes of the type [Cp*-  
(Me3P)2RudSi(SR)2][BPh4] thermally decompose via  
phenyl transfer from the BPh4 anion. For example,  
when [Cp*(Me3P)2RudSi[S(p-Tol)]2][BPh4] (21) is heated  
to 120 °C in a o-dichlorobenzene solution, complete  
conversion to Cp*(Me3P)2RuSi[S(p-Tol)]2Ph (26) within  
10 min is observed (by 31P NMR spectroscopy). Com-  
1
pound 26 was identified by comparison of H and 31P  
NMR spectra with those for an authentic sample.  
.
by addition of a nBu2O solution of LiB(C6F5)4 OEt2 to a  
(38) Albright, T. A.; Burdett, J . K.; Whangbo, M.-W. Orbital Interac-  
tions in Chemistry; Wiley-Interscience: New York: 1985.  
(39) Recent calculations at the RHF level of theory indicate that  
this twist of 34° is electronically preferred: Arnold, F. P. Unpublished  
results.  
(36) Straus, D. A.; Zhang, C.; Tilley, T. D. J . Organomet. Chem.  
1989, 369, C13.  
(37) Massey, A. G.; Park, A. J . J . Organomet. Chem. 1964, 2, 245.  
5612 Organometallics, Vol. 17, No. 26, 1998  
Grumbine et al.  
Similarly, attempts to generate [Cp*(Me3P)2RudSiMe2]-  
[BPh4] are complicated by the low solubility for the  
NaBPh4 reagent, which results in a slow reaction with  
Cp*(Me3P)2RuSiMe2OTf in dichloromethane-d2 to pro-  
duce thermally unstable [Cp*(Me3P)2RudSiMe2][BPh4]  
(over 3 days, as monitored by 31P NMR spectroscopy).  
The latter silylene complex decomposes to Cp*(Me3P)2-  
RuSiMe2Ph (27) (75-95%) as it is produced.  
R ea ct ion s of Silylen e Com p lexes w it h Lew is  
Ba ses. We have previously reported the interactions  
of silylene complexes with nitrogen-based donors such  
as acetonitrile and 4-(dimethylamino)pyridine (DMAP).20  
Generally, it is found that adducts of the type [Cp*-  
(Me3P)2RuSiX2(base)]+ form readily, and the stability  
of these adducts appears to correlate with the strength  
of the donor-acceptor interaction.20c Thus, the DMAP  
adduct [Cp*(Me3P)2RuSiMe2(DMAP)][BPh4] is excep-  
tionally stable.20c Such adducts tend to thermally  
decompose via elimination of the silylene group, with  
formation of a [Cp*(Me3P)2Ru(base)]+ cation. It remains  
unclear whether these decompositions proceed via dis-  
sociation of silylene from the base-free complex (which  
is in equilibrium with the adduct) or via dissociation of  
the silylene adduct :SiX2(base).20c  
There is a marked difference in stability between the  
nitrogen-donor-stabilized compounds reported previ-  
ously and the phosphine adducts described here. For  
example, the stabilized silylene complex [Cp*(Me3P)2-  
RuSiMe2(NCMe)][BPh4] has a half-life of about 17 days  
in dichloromethane, and [Cp*(Me3P)2RuSiMe2(DMAP)]-  
[BPh4] is similarly stable (3% decomposition after 1 day  
in dichloromethane-d2).20c Although the reasons for this  
difference in stability are not yet fully understood, it  
appears that the strength of the donor-acceptor inter-  
action plays an important role.  
The ylide CH2PPh3 reacts rapidly with 24 to form a  
single product (32a ), isolated as yellow crystals in 80%  
yield (eq 9). Likewise, the complex Cp*(Me3P)2RuSiMe2-  
OTf reacts with CH2PPh3 to form the analogous triflate  
salt 32b. Compounds 32a and 32b display remarkable  
stabilities, exhibiting no decomposition after 1 week in  
dichloromethane-d2 at room temperature (by 1H and 31P  
NMR spectroscopy). Heating a toluene solution of 32a  
for 1 day at 100 °C, however, resulted in decomposition  
1
to many products. The H NMR spectra reveal equiva-  
lent SiMe groups, and the 31P NMR spectra display a  
single resonance for the PMe3 ligands, indicating the  
presence of a molecular plane of symmetry. The connec-  
tivity depicted in eq 9 was confirmed by a single-crystal  
X-ray diffraction study of 32b (vide infra). The 29Si  
Compound 24 reacts quantitatively with 1 equiv of  
PMe3 or PPh3 in dichloromethane-d2 to form the base-  
stabilized silylene complexes [Cp*(Me3P)2RuSiMe2(PR3)]-  
1
[B(C6F5)4] (28, R ) Me; 29, R ) Ph), identified by H  
and 31P NMR spectroscopy. The 31P NMR spectra of  
both complexes contain two inequivalent phosphorus  
resonances in a 2:1 ratio, and the SiMe resonance for  
3
each is split into a doublet with J PH ) 4.5 Hz.  
Unfortunately, the thermal instability of 28 and 29  
prevented their isolation and full characterization. In  
dichloromethane solution, 28 decomposes (t1/2 ≈ 5 h at  
0 °C) to [Cp*(Me3P)3Ru][B(C6F5)4] (30, confirmed by  
independent synthesis of [Cp*(Me3P)3Ru][OTf]) as the  
only phosphorus-containing product. In addition, 29  
cleanly decomposes (t1/2 ≈ 5 h at 0 °C) to [Cp*(Me3P)2-  
1
RuPPh3][B(C6F5)4] (31, by H and 31P NMR spectros-  
copy). Presumably, both 28 and 29 decompose via  
extrusion and rapid oligomerization of the silylene  
fragment (eq 8). Consistent with this is the appearance  
spectrum contains a triplet of doublets (2J SiP ) 32 and  
15 Hz for the triplet and doublet, respectively) centered  
at 35.24 ppm, a shift of 276.17 ppm upfield from the  
resonance of 24. Such an upfield chemical shift indi-  
cates little, if any, silylene character in the bonding of  
32b and is more characteristic for a saturated Ru(II)  
silyl complex.  
The molecular structure of the cation in 32b is shown  
in Figure 2. Ruthenium adopts a three-legged piano  
stool geometry, with the phosphine and silyl groups  
approximately evenly distributed about the metal. The  
Ru-Si bond length of 2.381(2) Å is slightly longer than  
the analogous separation in the base-stabilized silylene  
complex [Cp*(Me3P)2RuSiPh2(NCMe)][BPh4] (2.328(2)  
Å)20a,b and is comparable to the corresponding distance  
in Cp*(Me3P)2RuSiPh2H (2.387(5) Å).20b The silicon  
atom is in a pseudo-tetrahedral environment, with  
distances of 1.920(9) and 1.899(9) Å to the two methyl  
carbon atoms and a somewhat longer distance of 1.976-  
(7) Å to the ylide carbon atom. The C(19)-P(3) distance  
of 1.779(6) Å is considerably longer than the 1.692(3) Å  
CdP distance in free CH2PPh3,40 indicating significant  
loss of double-bond character in the ylide upon coordi-  
in the 1H NMR spectra of several resonances in the  
region of δ 0.0-0.2. However, when 28 decomposed in  
the presence of the known silylene trapping agents  
HSiEt3 and HSi(SiMe3)3,2e the respective insertion  
products HSiMe2SiEt3 and HSiMe2Si(SiMe3)3 were not  
1
observed by H NMR spectroscopy nor GC/MS.  
Ruthenium Silylene Complexes  
Organometallics, Vol. 17, No. 26, 1998 5613  
Ta ble 4. Su m m a r y of Cr ysta llogr a p h ic Da ta for 24  
a n d 32b‚CH2Cl2  
24  
32b‚CH2Cl2  
formula  
C42H39BF20P2RuSi C39H58Cl2F3P3RuSSi  
fw  
1125.6  
956.93  
cryst color, habit  
cryst size, mm  
cryst syst  
space group  
a, Å  
yellow block  
yellow trapezoidal  
0.30 × 0.34 × 0.34 0.15 × 0.20 × 0.30  
monoclinic  
P21/n (No. 14)  
13.577(2)  
22.314(4)  
15.423(3)  
94.44(2)  
4658.4(15)  
4
monoclinic  
P21 (No. 4)  
10.1344(3)  
14.7333(4)  
15.1684(5)  
95.183(1)  
2255.6(1)  
2
1.409  
8.06  
908.00  
157  
b, Å  
c, Å  
â, deg  
V, Å3  
Z
D(calc), g cm-3  
µ (Mo KR), cm-1  
F(000)  
1.605  
5.42  
2256  
240  
F igu r e 2. ORTEP view of the cation in [Cp*(Me3P)2-  
RuSiMe2(CH2PPh3)]OTf (32b).  
temp, K  
2θmax, deg  
50.0  
8444  
46.5  
9339  
3557  
477  
total no. of data  
Ta ble 3. Selected Bon d Dista n ces (Å) a n d An gles  
no. of unique obsd data 4112  
no. of variables  
(d eg) for 32b‚CH2Cl2  
604  
R(int)  
0.0265  
0.032  
2.75  
4.1  
5.0  
(a) Bond Distances  
goodness of fit indicator 1.31  
R(F), %  
R(wF), %  
Ru-P(1)  
Ru-P(2)  
Ru-Si  
Si-C(17)  
Si-C(18)  
2.261(2)  
2.273(2)  
2.381(2)  
1.920(9)  
1.899(9)  
Si-C(19)  
1.976(7)  
1.779(6)  
1.796(8)  
1.805(8)  
1.811(7)  
5.78  
7.46  
0.80/-0.52  
P(3)-C(19)  
P(3)-C(20)  
P(3)-C(26)  
P(3)-C(32)  
max./min. residual  
0.93/-1.01  
density, e Å-3  
(b) Bond Angles  
92.71(8)  
silane independently from H2SiCl2, HSEt and NEt3,  
which resulted in the isolation of HSi(SEt)3.41 This type  
P(1)-Ru-P(2)  
P(1)-Ru-Si  
C(18)-Si-C(19)  
C(19)-P(3)-C(20)  
C(19)-P(3)-C(26)  
C(19)-P(3)-C(32)  
C(20)-P(3)-C(26)  
C(20)-P(3)-C(32)  
C(26)-P(3)-C(32)  
P(3)-C(19)-Si  
103.4(4)  
111.9(4)  
110.0(4)  
108.4(3)  
110.9(4)  
106.1(4)  
109.4(4)  
126.8(3)  
94.83(8)  
89.51(6)  
116.1(3)  
125.7(3)  
108.1(2)  
97.7(4)  
P(2)-Ru-Si  
Ru-Si-C(17)  
Ru-Si-C(18)  
Ru-Si-C(19)  
C(17)-Si-C(18)  
C(17)-Si-C(19)  
103.3(4)  
nation to silicon. The adducts 32a and 32b are there-  
fore best viewed as ruthenium silyl complexes of the  
type Cp*(Me3P)2RuSiR2R′, with the positive charge  
localized on the phosphonium phosphorus atom.  
Rea ction s of Silylen e Com p lexes w ith Hyd r ogen  
a n d Hyd r osila n es. Many of the hypothetical catalytic  
cycles that have been proposed in the context of inter-  
mediate silylene complexes involve hydrogen and/or  
hydrosilanes as reagents or products.1 It is therefore  
of interest to characterize the reactivity of isolated silyl-  
ene complexes toward these small molecules. Note that  
we have previously shown that silylene complexes of the  
type [Cp*(Me3P)2RudSiX2]+ exhibit low reactivities  
toward nonpolar unsaturated substrates, probably due  
to the coordinatively saturated nature of the ruthenium  
center.24a  
of redistribution reaction of thiosilanes has also been  
observed for the silane Cl2Si(SMes)2.5e  
Reaction of 24 with H2 (1 atm) at -78 °C in dichlo-  
romethane-d2 led to a mixture of products that included  
1
30, 33, and 34 (eq 11).24a The H NMR spectra of the  
The reaction of [Cp*(Me3P)2RuSi(SEt)2]BPh4 (20) with  
H2 (1 atm) in dichloromethane-d2 resulted in slow  
conversion to a ruthenium hydride complex 33 (δRuH  
)
-10.04; 35% conversion after 9 h) and the silane HSi-  
(SEt)3 (by NMR spectroscopy and GC/MS). A prepara-  
tive scale reaction (50 psi H2) generated isolable quan-  
tities of 33, which was characterized as the hydride  
complex shown in eq 10. The latter compound exhibits  
a triplet in the 31P NMR spectrum (2J PH ) 33 Hz) due  
to coupling to equivalent hydride ligands, after selective  
decoupling of the methyl protons. The HSi(SEt)3 may  
result from redistribution of the kinetic product H2Si-  
(SEt)2, as was observed in attempts to prepare this  
reaction mixture showed that the SiMe resonances for  
24 diminished over the course of 4 days and were  
replaced by various peaks in the δ 0.0-0.2 region,  
presumably representing species derived from the dis-  
placed silylene fragment. Although the hydride ligands  
(40) Schmidbaur, H.; J eong, J .; Schier, A.; Graf, W.; Wilkinson, D.  
L.; Mu¨ller, G.; Kru¨ger, C. New J . Chem. 1989, 13, 341.  
(41) Grumbine, S. K., Ph.D. Thesis, UC San Diego, 1993.  
5614 Organometallics, Vol. 17, No. 26, 1998  
Grumbine et al.  
of 33 and 34 are most likely derived from H2, no  
formation of H2SiMe2 was detected (by H NMR spec-  
troscopy and GC/MS).  
and a silyl hydride complex of the type [Cp*(Me3P)2Ru-  
(H)(SiH2R)]+. When R ) Mes, these products react fur-  
ther to produce H2SiMes(SEt), by an unknown mecha-  
nism.  
1
The reaction of 20 with H3SiSiPh3 in dichloromethane-  
d2 proceeded slowly (75% conversion after 3 days) to one  
ruthenium product and two main Si-H products, one  
of which is HSi(SEt)3. In a scaled-up version of this  
reaction, the new product [Cp*(Me3P)2Ru(H)(SiH2SiPh3)]-  
[BPh4] (35) was crystallized from the reaction mixture  
As with the reaction of 24 with H2, reactions of 24  
with H2SiPh2, HSiEt3, and HSi(SiMe)3 in dichloro-  
methane-d2 at 0 °C gave a complex mixture of products  
1
consisting primarily of 30, 33, and 34 (by H and 31P  
NMR spectroscopy). The chloride ligand of 34 is pre-  
sumed to originate from the solvent, and no redistribu-  
tion or Si-Si bond formation was observed.  
1
in 24% yield (eq 12). The Si-H H NMR resonance for  
Con clu d in g Rem a r k s  
In this paper we have described a synthetic route to  
ruthenium silylene complexes of the type [Cp*(Me3P)2-  
RudSiX2]+. This method works well in selected cases,  
where X ) thiolate, Me, or Ph, but so far has not proven  
successful with a number of other substituents at sili-  
con. The key precursor compounds in this approach are  
triflato(silyl) derivatives of the type Cp*(Me3P)2RuSiX2-  
OTf, which possess labile triflate groups. In solution,  
the triflate may be exchanged for less coordinating an-  
ions that result in stabilization of the three-coordinate  
silicon compounds. In one case, this exchange was suc-  
cessful with use of a starting silyl chloride derivative  
(6), presumably because a relatively stable silylene  
complex, [Cp*(Me3P)2RuSi(SCy)2][BPh4] (22), is formed.  
Note that the BPh4- anion is compatible with thiolate-  
substituted silylene complexes, but isolation of the less  
stable dimethyl- and diphenylsilylene complexes (24 and  
25) requires use of the more inert anion B(C6F5)4-. The  
silylene complexes reported here are characterized by  
highly downfield-shifted 29Si NMR resonances in the re-  
gion δ 250-310. These shift values are consistent with  
others that have been characterized for silylene com-  
plexes, including [trans-(Cy3P)2(H)PtSi(SEt)2][BPh4] (δ  
308.65),22c [(iPr2PCH2CH2PiPr2)(H)PtdSiMes2][BMe-  
(C6F5)3] (δ 338.5),22e (Cy3P)2PtdSiMes2 (δ 358),22f and  
(iPr3P)2PtdSiMes2 (δ 367).22f The complete characteriza-  
tion of 20-25 represents a significant advance in the  
development of transition metal-silylene chemistry.  
Now that stable examples with a number of substitution  
patterns are known, it is clear that such species are  
viable synthetic targets and reasonable chemical inter-  
mediates.  
Many of the reactions observed for silylene complexes  
reflect the presence of a highly electrophilic silicon cen-  
ter. Thus, the silylene complexes reported here readily  
form adducts with a number of Lewis bases. It is inter-  
esting to compare the structural and spectroscopic prop-  
erties for adducts of these types, which have often been  
described as having considerable silylene character,  
with authentic silylene complexes possessing sp2 silicon.  
This comparison shows that the “donor-stabilized” si-  
lylene complexes possess structural and spectroscopic  
properties that are much more similar to metal silyl  
complexes and reflect the presence of sp3 silicon. This  
is perhaps dramatically illustrated by formation of the  
ylide “adduct” 32, which exhibits structural parameters  
and an 29Si NMR shift that are highly consistent with  
a simple ruthenium silyl complex. Similar observations  
for other donor-stabilized silylene complexes3,5,14-17,20  
suggest that these compounds are also best represented  
by resonance structures reflecting tetrahedral silicon  
centers with four covalent bonds (e.g., structures A-E).  
this compound appeared as a virtual triplet at δ 3.81,  
and the hydride ligand appeared as a triplet at δ -10.10  
(J PH ) 9 Hz). The volatile products from the reaction  
mixture were found to contain mainly HSi(SEt)3 (by 1H  
NMR and mass spectrometry). Thus, it appears that  
this reaction is also complicated by a redistribution at  
silicon.  
The reaction of 20 with H3SiMes proceeds very slowly  
(70% conversion after 7 h in dichloromethane-d2) to a  
mixture of products (eq 13). The hydride 34 and BPh3  
were isolated from the reaction mixture in 34% and 24%  
yields, respectively. In addition, the major silane prod-  
uct was identified as H2SiMes(SEt), by comparison of  
1
its H, 13C, 29Si NMR and mass spectra to those for an  
independently prepared sample. Monitoring the reac-  
1
tion by H NMR spectroscopy provided evidence for an  
intermediate in this transformation, characterized by  
3
triplet resonances assigned to RuSiH (δ 4.69, J PH ) 8  
2
Hz) and RuH (δ -11.23, J PH ) 9 Hz) groups. After  
speculating that this intermediate might be analogous  
to 35, we generated [Cp*(Me3P)2Ru(H)(SiH2Mes)][BPh4]  
(36) independently via reaction of [Cp*(Me3P)2Ru(NCMe)]-  
[BPh4] with 1 equiv of H3SiMes in dichloromethane-d2.  
Compound 36, which exists in a 1:12 equilibrium with  
[Cp*(Me3P)2Ru(NCMe)][BPh4], was identified as the in-  
termediate indicated in eq 13. To the solution contain-  
ing 36 was added HSi(SEt)3, and after 6 days the main  
1
SiH-containing product was H2SiMes(SEt) (90% by H  
and 29Si NMR spectroscopy). It therefore seems that  
reactions of 20 with H3SiSiPh3 and H3SiMes proceed  
via similar pathways that initially produce HSi(SEt)3  
Ruthenium Silylene Complexes  
Organometallics, Vol. 17, No. 26, 1998 5615  
(2.1 mL, 21 mmol), and HS(2-Naph) (10 g, 62 mmol). The  
silane was crystallized from diethyl ether at -35 °C. Yield:  
0.92 g/9% (not optimized). MS (EI) parent ion: calcd m/e 506;  
found m/e 506. 1H NMR (benzene-d6): δ 6.20 (s, 1 H, SiH),  
7.15 (m, 2 H, Naph), 7.29 (m, 2 H, Naph), 7.45 (m, 2 H, Naph),  
7.85 (s, 1 H, Naph).  
HSi(SCy)3/HSi(SCy)2Cl Mixtu r e (4:1). The procedure for  
HSi(SEt)3 was followed, using NEt3 (8.1 mL, 60 mmol), diethyl  
ether (800 mL), HSiCl3 (2.3 mL, 23 mmol), and HSCy (5.4 mL,  
44 mmol). The silane was isolated by filtration (from HNEt3-  
Cl) followed by vacuum distillation (bp 145-180 °C/0.1 Torr).  
Yield: 2.5 g. 1H NMR (benzene-d6): δ 0.9-1.3 (m, SCy, di  
and tri), 1.78 (m, SCy, di), 1.95 (m, SCy, tri), 2.98 (m, SCy,  
di), 3.16 (m, SCy, tri), 5.87 (s, SiH, di), 6.14 (s, SiH, tri).  
Finally, initial reactivity studies with the ruthenium  
silylene complexes reported here demonstrate that they  
are relatively unreactive toward nonpolar substrates  
such as hydrosilanes and hydrogen. This appears to  
reflect the coordinative saturation of the metal center,  
and in fact in other studies we have observed that the  
16-electron silylene complex (Cy3P)2PtdSiMes2 reacts  
more readily with hydrogen.22f  
HSi(SMes)3/HSi(SMes)2Cl Mixt u r e (4:1). The above  
procedure was employed, starting with 3.0 equiv of HSMes.  
The product mixture crystallized from diethyl ether as a  
mixture of HSi(SMes)3 and HSi(SMes)2Cl (4:1 ratio). 1H NMR  
(benzene-d6) HSi(SMes)2Cl: δ 1.98 (s, 6 H, C6Me2H2Me), 2.36  
(s, 12 H, C6Me2H2Me), 5.73 (s, 1 H, SiH), 6.68 (s, 4 H, C6Me2H2-  
Me). HSi(SMes)3: δ 2.00 (s, 9 H, C6Me2H2Me), 2.32 (s, 18 H,  
C6Me2H2Me), 5.27 (s, 1 H, SiH), 6.69 (s, 6 H, C6Me2H2Me).  
HSi(SCH2CH2CH2S)P h . The procedure for HSi(SEt)3 was  
followed, using NEt3 (7.3 mL, 55 mmol), diethyl ether (600  
mL), HSiCl2Ph (4.0 mL, 14 mmol), and HS(CH2)3SH (1.4 mL,  
14 mmol). Evaporation of the diethyl ether solvent produced  
the product as a reasonably pure, viscous liquid. Yield: 55%.  
MS (EI) parent ion: calcd m/e 211; found m/e 211.  
Exp er im en ta l Section  
Gen er a l P r oced u r es. Manipulations were performed un-  
der an inert atmosphere of nitrogen or argon. Dry, oxygen-  
free solvents were employed throughout. Elemental analyses  
were performed by Pascher Analytical Laboratories, Desert  
Analytics, and the UC Berkeley College of Chemistry Micro-  
analytical Facility. All NMR spectra were recorded at room  
temperature unless otherwise indicated. 29Si NMR spectra  
were obtained on a GE QE-300 or a Bruker AM 300 instrument  
at 59.6 MHz, using single-pulse techniques (typically with a  
2-4 s delay time and ca. 10 000 transients) or DEPT. 1H, 13C,  
and 31P NMR spectra were obtained at 300, 75.5, and 121.5  
MHz, respectively, unless otherwise noted. Infrared spectra  
were recorded on a Perkin-Elmer 1330 infrared spectrometer as  
Nujol mulls on CsI plates, unless otherwise indicated, and all  
absorptions are reported in cm-1. Conductivity measurements  
Cp *(Me3P )2Ru SiCl3 (1). Cp*(Me3P)2RuCH2SiMe3 (1.5 g,  
3.2 mmol), HSiCl3 (0.33 mL, 3.4 mmol), PMe3 (0.054 mL, 0.7  
mmol), and toluene (40 mL) were added to a flask equipped  
with a Teflon valve. The flask was closed and heated to 130  
°C for 12 h, which resulted in precipitation of the product. After  
removing the volatile materials in vacuo, the precipitate was  
washed with pentane (10 mL) and extracted with benzene (3  
× 40 mL). After removing the benzene from the combined  
extracts, the remaining solid was extracted again with 3 × 15  
mL of benzene. The combined extracts were evaporated to dry-  
ness to give a slightly yellow precipitate. Yield: 0.36 g, 22%.  
Anal. Calcd for C16H33Cl3P2RuSi: C, 36.8; H, 6.36. Found: C,  
37.1; H, 6.38. 1H NMR (benzene-d6): δ 1.18 (vir t, 18 H, PMe3),  
1.58 (t, J HP ) 1 Hz, 15 H, C5Me5). 13C{1H} NMR (benzene-  
d6): δ 11.44 (C5Me5), 22.90 (vir t, PMe3), 95.25 (C5Me5). 31P-  
{1H} NMR (benzene-d6): δ 3.33. 29Si{1H} NMR (benzene-d6):  
were acquired with a YSI model 3S conductance meter. The  
compounds HSMes,42 LiB(C6F5)4‚Et2O,37 B(C6F5)3,43 NaC2B9H12  
,
44  
Ph3CBPh4,36 NaB[3,5-(CF3)2C6H3]4,45 NaPh3BNCBPh3,46 and  
47  
NaCo(C2B9H12  
)
2
were prepared by literature methods. The  
2
complex [Cp*(Me3P)2Ru(NCMe)][BPh4] was prepared by the  
reaction of Cp*(Me3P)2RuCl27 with AgBPh4 in acetonitrile.  
HSi(SEt)3. NEt3 (32 mL, 240 mmol) was added to a 1 L  
flask containing diethyl ether (800 mL), HSiCl3 (8.0 mL, 80  
mmol), and HSEt (18 mL, 240 mmol). A large volume of white  
precipitate (HNEt3Cl) formed, creating a viscous solution that  
was stirred for 10 h. The reaction was then filtered, and the  
solid was extracted with 200 mL of diethyl ether. The  
combined diethyl ether solutions were concentrated to an oil,  
and vacuum distillation (bp 110-113 °C/0.01 Torr) gave 10 g  
of the product (59%). GC/MS (EI) parent ion: calcd m/e 212;  
found m/e 212. 1H NMR (benzene-d6): δ 1.13 (t, J ) 8 Hz, 9  
H, SCH2CH3), 2.55 (q, J ) 8 Hz, 6 H, SCH2CH3), 5.89 (s, 1 H,  
SiH). 13C{1H} NMR (benzene-d6): δ 17.16 (SCH2CH3), 22.42  
(SCH2CH3). 29Si{1H} NMR (benzene-d6): δ 12.12 (s).  
δ 42.69 (t, J SiP ) 38 Hz). IR: 1300 w, 1271 m, 1065 w, 1023  
m, 956 s, 939 s, 855 m, 715 s, 619 m, 486 vs, 433 vs.  
Cp*(Me3P )2Ru Si(NMe2)3 (2). Cp*(Me3P)2RuCH2SiMe3 (0.28  
g, 0.59 mmol) and HSi(NMe2)3 (0.29 mL, 1.5 mmol) were  
heated (90 °C) in a closed flask for 12 h with stirring. The  
resulting solid was exposed to vacuum to remove the volatile  
materials and then extracted into pentane (20 mL). After  
concentrating to 1 mL and cooling to -35 °C, light yellow  
crystals formed (0.21 g; 64%). When the reaction was carried  
out in toluene, the only product isolated was Cp*(Me3P)2Ru-  
(m/ p-Tol). Anal. Calcd for C22H51P2RuN3Si: C, 48.2; H, 9.37;  
N, 7.65. Found: C, 48.2; H, 9.29; N, 7.64. 1H NMR (benzene-  
d6): δ 1.22 (vir t, 18 H, PMe3), 1.66 (t, J HP ) 1 Hz, 15 H, C5-  
Me5), 2.74 (br s, 18 H, NMe2). 13C{1H} NMR (benzene-d6): δ  
11.93 (C5Me5), 24.61 (vir t, PMe3), 42.45 (NMe2), 93.88 (C5Me5).  
31P{1H} NMR (benzene-d6): δ 5.40. IR: 1292 m, 1224 s, 1210  
s, 1180 s, 1135 w, 1060 m, 985 s, 964 s, 938 s, 847 m, 700 m,  
667 m, 642 m, 620 m, 600 s, 584 s, 462 m.  
HSi(S-2-Na p h )3. The procedure for HSi(SEt)3 was followed,  
using NEt3 (12 mL, 90 mmol), diethyl ether (300 mL), HSiCl3  
(42) Szmuszkovicz, J . Org. Prep. Proced. 1969, 1, 43.  
(43) Massey, A. G.; Park, A. J . J . Organomet. Chem. 1966, 5, 218.  
(44) Plesek, J .; Hermanek, S.; Stibr, B. Inorg. Synth. 1983, 22, 231.  
(45) Nishida, H.; Takada, N.; Yoshimur, M.; Sonoda, T.; Kobayashi,  
H. Bull. Chem. Soc. J pn. 1984, 57, 2600.  
(46) Giandomenico, C. M.; Dewan, J . C.; Lippard, S. J . J . Am. Chem.  
Soc. 1981, 99, 1406.  
(47) Hawthorne, M. F.; Andrews, T. D.; Garrett, P. M.; Olsen, F. P.;  
Reintjes, M.; Tebbe, R. N.; Warren, L. F.; Wegner, P. A.; Young, D. C.  
Inorg. Synth. 1967, 10, 91.  
Cp *(Me3P )2Ru Si(SEt)3 (3). This compound was prepared  
by the procedure reported for Cp*(PMe3)2RuSi[S(p-Tol)]3.20c  
Yield: 74% of yellow crystals, mp 190-195 °C. Anal. Calcd  
for C22H48P2RuS3Si: C, 44.1; H, 8.00. Found: C, 44.1; H, 8.20.  
1H NMR (benzene-d6): δ 1.37 (virtual t, 18 H, PMe3), 1.41 (t,  
J ) 7 Hz, 9 H, SCH2CH3), 1.80 (s, 15 H, C5Me5), 2.99 (q, J )  
7 Hz, 6 H, SCH2CH3). 13C NMR (dichloromethane-d2): δ 12.23  
(q, J CH ) 127 Hz, C5Me5), 18.28 (q, J ) 127 Hz, SCH2CH3),  
5616 Organometallics, Vol. 17, No. 26, 1998  
Grumbine et al.  
23.81 (br q, J ) 127 Hz, PMe3), 26.21 (t, J CH ) 135 Hz, SCH2-  
CH3), 94.74 (s, C5Me5). 31P{1H} NMR (benzene-d6): δ 3.04.  
29Si NMR (dichloromethane-d2): δ 60.34 (t, J SiP ) 34 Hz). IR:  
1292 m, 1276 m, 1250 m, 1063 w, 1022 w, 953 s, 938 s, 852 w,  
708 m, 663 m.  
chloride), and the resulting mixture was heated (115 °C) in a  
closed flask for 5 h. After removing the volatile material in  
vacuo and washing with pentane (3 × 20 mL), the product  
was crystallized from a 1:1 dichloromethane/diethyl ether  
mixture at -78 °C. Yield: 35% (0.57 g). Anal. Calcd for  
C34H55ClP2RuS2Si: C, 54.1; H, 7.35; Cl, 4.70. Found: C, 53.6;  
H, 7.37; Cl, 4.56. Mp: 232-234 °C, dec 1H NMR (dichlo-  
romethane-d2): δ 1.47 (virtual t, 18 H, PMe3), 1.95 (s, 15 H,  
Cp*), 2.18 (s, 6 H, SC6Me2H2Me), 2.28 (s, 12 H, SC6Me2H2Me),  
6.75 (s, 4 H, SC6Me2H2Me). 31P{1H} NMR (dichloromethane-  
d2): δ 3.96. IR: 1298 m, 1279 m, 1048 w, 1023 w, 955 s, 940  
s, 849 s, 710 m, 675 w, 665 w, 458 s.  
Cp *(Me3P )2Ru Si(S-2-Na p h )3 (4). Toluene (20 mL) was  
added to Cp*(Me3P)2RuCH2SiMe3 (1.36 g, 2.86 mmol) and HSi-  
(S-2-Naph)3 (1.39 g, 2.86 mmol), and the resulting solution was  
stirred and heated (100 °C) in a closed flask for 5 h. After  
removing the volatile materials in vacuo, the solid was washed  
with diethyl ether (3 × 15 mL) and was then extracted into  
dichloromethane (3 × 30 mL). The combined extracts were  
reduced in volume and cooled to -35 °C to afford yellow  
crystals. A second crop was obtained by reducing the volume  
further and cooling to -35 °C. Total yield ) 1.45 g, 57%. Anal.  
Calcd for C46H54P2RuS3Si: C, 61.8; H, 6.09. Found: C, 61.0;  
H, 5.95. Mp: 198-205 °C (dec). 1H NMR (dichloromethane-  
d2): δ 1.57 (vir t, 18 H, PMe3), 1.97 (t, J HP ) 1 Hz, 15 H, C5Me5),  
6.85 (d, J ) 8 Hz, 3 H, Naph), 7.14-7.41 (m, 15 H, Naph),  
7.56 (d, J ) 8 Hz, 3 H, Naph). 13C{1H} NMR (dichlo-  
romethane-d2): δ 12.37 (C5Me5), 24.33 (vir t, PMe3), 95.62 (C5-  
Me5), 125.24, 125.71, 126.93, 127.49, 127.85, 128.17, 131.87,  
132.89, 133.06, 135.45 (aryl carbons). 31P{1H} NMR (dichlo-  
romethane-d2): δ 2.32. IR: 1300 m, 1228 m, 1218 m, 1128  
m, 1067 m, 1067 w, 1019 w, 952 br s, 936 br s, 897 m, 859 m,  
845 m, 812 s, 741 s, 720 m, 471 w, 430 br s.  
Cp *(Me3P )2Ru Si(SEt)2OTf (8). To a solution of 3 (2.80  
g, 4.67 mmol) in pentane (20 mL) was added Me3SiOTf (0.85  
mL, 4.67 mmol). This mixture was stirred for 8 h, during  
which time the product precipitated as yellow microcrystals.  
The supernatant was removed by filtration and the product  
was washed with pentane (5 mL) to afford 2.91 g of 8 (91%  
yield; mp 173-179 °C dec). Anal. Calcd for C21H43F3O3P2RuS3-  
Si: C, 36.7; H, 6.30. Found: C, 36.7; H, 6.54. 1H NMR (di-  
chloromethane-d2): δ 1.26 (t, J ) 7 Hz, 6 H, SCH2CH3), 1.46  
(virtual t, 18 H, PMe3), 1.80 (s, 15 H, Cp*), 2.88 (q, J ) 7 Hz,  
4 H, SCH2CH3). 13C{1H} NMR (dichloromethane-d2): δ 11.52  
(C5Me5), 17.50 (SCH2CH3), 23.87 (t, J CP ) 15 Hz, PMe3), 26.28  
(SCH2CH3), 94.26 (C5Me5). 31P{1H} NMR (dichloromethane-  
d2): δ 2.07. 29Si NMR (-80 °C, dichloromethane-d2): δ 86.05  
(t, J SiP ) 37 Hz). IR: 1358 s, 1281 w, 1235 m, 1208 s, 1172 s,  
1152 m, 955 s, 938 s, 850 w, 712 w, 664 w, 628 s. Equivalent  
conductance ) 12 Ω-1 cm2 equiv-1 (0.0018 M at 23 °C in  
dichloromethane).  
Cp *(Me3P )2R u Si(SCH2CH2CH2S)P h (5). Toluene (15  
mL) was added to Cp*(PMe3)2RuCH2SiMe3 (1.8 g, 2.1 mmol)  
and HSi(SCH2CH2CH2S)Ph (1.3 g, 2.1 mmol), and the resulting  
solution was heated (120 °C) in a closed flask for 12 h. After  
removing the volatile materials by vacuum transfer, the  
resulting solid was extracted into diethyl ether, and then  
pentane was added until the solution became cloudy. Two  
types of crystals formed upon cooling to -35 °C, which were  
separated by hand and determined (by 1H and 31P NMR  
spectroscopy) to be the starting material, Cp*(Me3P)2RuCH2-  
SiMe3, and the new product 5. Yield: 0.42 g, 34%. Anal. Calcd  
for C25H44P2RuS2Si: C, 50.1; H, 7.40. Found: C, 49.8; H, 7.49.  
1H NMR (benzene-d6): δ 1.43 (vir t, 18 H, PMe3), 1.52 (s, 15  
H, C5Me5), 2.00 (m, 2 H, CH2CH2CH2), 2.69 (m, 4 H, CH2-  
CH2CH2), 7.72 (t, J ) 7 Hz, 2 H, Ph), 7.39 (t, J ) 7 Hz, 2 H,  
Ph), 8.35 (d, J ) 7 Hz, 1 H, Ph). 13C{1H} NMR (benzene-d6):  
δ 11.70 (C5Me5), 24.76 (vir t, PMe3), 28.72 (CH2CH2CH2), 31.80  
(CH2CH2CH2), 93.83 (C5Me5), 126.69, 127.34, 136.81, 147.16  
(phenyl). 31P{1H} NMR (23 °C, benzene-d6): δ 5.87. 29Si{1H}  
Cp*(Me3P )2Ru Si(NMe2)2(OTf) (13) an d Cp*(Me3P )2Ru Si-  
(NMe2)(OTf)2 (14). Trimethylsilyl triflate (0.12 mL, 0.7  
mmol) was added to a cold (-78 °C) pentane solution (100 mL)  
of Cp*(Me3P)2RuSi(NMe2)3 (0.61 g, 1.1 mmol), the resulting  
solution was allowed to slowly warm to 23 °C, and then stirring  
was continued for 12 h. The resulting precipitate was isolated  
by filtration and washed with pentane (3 mL) to give 0.12 g  
(17%) of product that contained a small amount of contamina-  
tion by 14. Anal. Calcd for C21H45F3P2RuN2O3SSi: C, 38.6;  
H, 6.94; N, 4.28. Found: C, 37.9; H, 6.29; N, 2.86. 1H NMR  
(dichloromethane-d2): δ 1.50 (vir t, 18 H, PMe3), 1.84 (t, J HP  
) 1 Hz, 15 H, C5Me5), 2.72 (s, 12 H, NMe2). 13C{1H} NMR  
(dichloromethane-d2): δ 11.31 (C5Me5), 24.17 (vir t, PMe3),  
40.06 (NMe2), 94.79 (C5Me5). 31P{1H} NMR (dichloromethane-  
d2): δ -1.38. IR: 1365 m, 1265 s, 1188 m, 1139 s, 1029 s,  
992 m, 978 m, 936 m, 720 m, 666 w, 633 s. To the filtrate  
from above, more trimethylsilyl triflate (0.36 mL, 2.1 mmol)  
was added, and the solution was then stirred for an additional  
12 h. The resulting precipitate (0.55 g) was isolated and then  
crystallized from a 1:1 dichloromethane/diethyl ether mixture  
at -35 °C to give yellow crystals of 14. Yield ) 0.18 g (22%).  
Anal. Calcd for C21H45F3P2RuN2O3SSi: C, 31.7; H, 5.18; N,  
1.85. Found: C, 31.3; H, 5.38; N, 2.23. 1H NMR (dichlorometh-  
ane-d2): δ 1.46 (vir t, 18 H, PMe3), 1.77 (t, J HP ) 1 Hz, 15 H,  
C5Me5), 2.66 (s, 6 H, NMe2). 13C{1H} NMR (dichloromethane-  
d2): δ 11.13 (C5Me5), 23.68 (vir t, PMe3), 39.34 (NMe2), 95.21  
(C5Me5). 31P{1H} NMR (dichloromethane-d2): δ -0.03. 29Si-  
2
NMR (benzene-d6): δ 48.23 (t, J SiP ) 29 Hz).  
Cp *(Me3P )2Ru Si(SCy)2Cl (6). Toluene (15 mL) was added  
to Cp*(Me3P)2RuCH2SiMe3 (0.80 g, 1.7 mmol) and the HSi-  
(SCy)3/HSi(SCy)2Cl (4:1) mixture (2.2 g, 1.4 mmol of HSi-  
(SCy)2Cl), and the resulting mixture was stirred with heating  
(120 °C) in a closed flask for 5 h, resulting in some precipita-  
tion. After removing the volatile material in vacuo, the  
precipitate was washed with pentane (2 × 10 mL). The  
remaining yellow powder was extracted into diethyl ether (15  
mL), and the resulting solution was cooled to -78 °C, resulting  
in 0.50 g of light yellow crystals. Yield: 52% (based on HSi-  
(SCy)2Cl). Anal. Calcd for C28H55ClP2RuS2Si: C, 49.3; H, 8.12.  
Found: C, 48.8; H, 8.07. Mp: 215-218 °C, dec. 1H NMR  
(dichloromethane-d2): δ 1.1-1.9 (m, 16 H, Cy), 1.46 (vir t, 18  
H, PMe3), 1.80 (s, 15 H, C5Me5), 2.07 (br m, 4 H, Cy), 3.15 (br  
m, 2 H, Cy). 13C{1H} NMR (dichloromethane-d2): δ 12.21  
(C5Me5), 23.55 (vir t, PMe3), 26.34, 27.24, 27.43, 37.61, 38.30,  
44.83 (Cy carbons), 95.06 (C5Me5). 31P{1H} NMR (dichlo-  
2
{1H} NMR (dichloromethane-d2): δ 37.88 (t, J SiP ) 41 Hz).  
IR: 1360 s ν(SO3), 1286 m 1240 m, 1195 s, 1150 m, 1002 s,  
972 m, 955 m, 924 m, 850 w, 712 w, 672 m, 629 s, 460 m.  
Cp *(Me3P )2R u Si(SCH 2CH 2S)S-p -Tol) (16). The com-  
pounds 15 (0.900 g, 1.08 mmol) and LiSCH2CH2SLi (0.266 g,  
2.17 mmol) were stirred together in toluene (40 mL) for 11  
days. The volatile materials were removed by vacuum distil-  
lation, and the resulting precipitate was then extracted with  
diethyl ether (2 × 25 mL). The combined ether extracts were  
cooled to -78 °C to obtain 0.116 g of product. After concen-  
trating the solution, a second crop of crystals (0.095 g) was  
obtained. Total yield: 31%. Anal. Calcd for C25H44P2RuS3-  
Si: C, 47.6; H, 7.03. Found: C, 47.9; H, 7.08. 1H NMR  
romethane-d2): δ 3.20. 29Si NMR (dichloromethane-d2):  
δ
67.57 (t, 2J SiP ) 40 Hz). IR: 1300 w, 1278 m, 1255 w, 1203 w,  
1025 w, 993 m, 959 s, 942 s, 882 w, 856 w, 842 w, 744 m, 710  
m, 673 w, 665 s, 483 m, 453 s, 420 m.  
Cp *(Me3P )2Ru Si(SMes)2Cl (7). Toluene (6 mL) was added  
to Cp*(Me3P)2RuCH2SiMe3 (1.02 g, 2.15 mmol) and a 4:1 HSi-  
(SMes)3/HSi(SMes)2Cl mixture (1.01 g, 2.26 mmol of the  
Ruthenium Silylene Complexes  
Organometallics, Vol. 17, No. 26, 1998 5617  
(dichloromethane-d2): δ 1.49 (vir t, 18 H, PMe3), 1.91 (s, 15  
H, C5Me5), 2.04 (m, 2 H, SCH2CH2S), 2.28 (s, 3 H, C6H4Me),  
2.44 (m, 2 H, SCH2SCH2S), 6.98 (d, J ) 8 Hz, 2 H, C6H4Me),  
7.37 (d, 2 H, J ) 8 Hz, C6H4Me). 13C{1H} NMR (dichlo-  
romethane-d2): δ 12.22 (C5Me5), 21.22 (C6H4Me), 23.33 (vir t,  
PMe3), 37.17 (SCH2CH2S), 95.12 (C5Me5), 128.57, 134.55,  
135.38, 135.98 (aryl carbons). 31P{1H} NMR (dichloromethane-  
d2): δ 3.63. 29Si{1H} NMR (dichloromethane-d2): δ 71.71 (t,  
2J SiP ) 34 Hz). IR: 1294 w, 1277 m, 1150 w, 1089 w, 1020 w,  
957 s, 941 s, 845 m, 800 s, 710 br m, 668 m, 472 s, 420 m.  
Cp *(Me3P )2Ru Si(1,2,4-S2MeC6H3)(S-p-Tol) (17). Ben-  
zene (30 mL) was added to a flask containing 15 (0.66 g, 0.79  
mmol) and Li2S2MeC6H3 (0.17 g, 1.0 mmol), and the resulting  
heterogeneous mixture was stirred for 36 h. The reaction  
mixture was filtered to remove precipitated LiOTf, and the  
filtrate was evacuated to a solid, which was extracted into  
diethyl ether (3 × 15 mL). Upon cooling the combined extracts  
to -78 °C, precipitation of the product as a yellow powder  
occurred (0.12 g). After concentrating and cooling the solution  
further, a second crop (0.16 g) was obtained. Total yield: 51%.  
Anal. Calcd for C30H46P2RuS3Si: C, 51.9; H, 6.68. Found: C,  
51.5; H, 6.98. 1H NMR (benzene-d6): δ 1.32 (vir t, 18 H, PMe3),  
1.82 (s, 15 H, C5Me5), 1.95 (s, 3 H), 1.98 (s, 3 H), 6.40 (d, J )  
8 Hz, 1 H, S2C6H3Me), 6.67 (d, J ) 8 Hz, 2 H, SC6H4Me), 7.05  
(s, 1 H, S2C6H3Me), 7.14 (d, J ) 8 Hz, 1 H, S2C6H3Me), 7.69  
(d, 2 H, J ) 8 Hz, SC6H4Me). 13C{1H} NMR (dichloromethane-  
d2): δ 12.04, 12.44 (C5Me5), 20.61 (C6H4Me), 23.40 (vir t, PMe3),  
95.03 (C5Me5), 123.48, 125.35, 126.42, 127.80, 128.74, 132.28,  
135.15, 135.34, 138.33, 141.63 (aryl carbons). 31P{1H} NMR  
(dichloromethane-d2): δ 3.63. 29Si{1H} NMR (dichloromethane-  
1067 w, 1028 w, 958 s, 935 s, 852 m, 841 m, 750 w, 731 s, 704  
s, 669 w, 664 w, 609 s, 561 s, 510 m. Equivalent conductance  
) 30 Ω-1 cm2 equiv-1 (0.0018 M at 23 °C in dichloromethane).  
Attempts to measure the molecular weight in dichloromethane  
were hindered by decomposition of the compound.  
[Cp *(Me3P )2Ru Si(S-p-Tol)2][BP h 4] (21). Compound 11  
(3.00 g, 3.69 mmol), NaBPh4 (1.50 g, 4.43 mmol), and dichlo-  
romethane (20 mL) were stirred in a reaction flask for 2 h.  
The solution was then filtered to remove the precipitate of  
NaOTf. The resulting solution was then concentrated, and  
diethyl ether was added to precipitate 21 as yellow microc-  
rystals in 58% yield (2.1 g; mp 91-95 °C dec). Anal. Calcd  
for C54H67BP2RuS2Si: C, 66.0; H, 6.87; S, 6.52. Found: C, 66.7;  
H, 7.11; S, 6.36. 1H NMR (dichloromethane-d2): δ 1.37 (virtual  
t, 18 H, PMe3), 1.91 (s, 15 H, Cp*), 2.34 (s, 6 H, SC6H4Me),  
6.89 (t, J ) 7 Hz, 4 H, BPh), 7.04 (t, J ) 7 Hz, 8 H, BPh), 7.14  
(d, J ) 8 Hz, 4 H, SC6H4Me), 7.21 (d, J ) 8 Hz, 4 H, SC6H4-  
Me), 7.31 (br s, 8 H, BPh). 13C{1H} NMR (dichloromethane-  
d2): δ 11.59 (s, C5Me5), 21.58 (s, SC6H4Me), 24.12 (t, J CP ) 16  
Hz, PMe3), 96.70 (s, C5Me5), 122.08, 125.98, 128.68, 130.79,  
134.54, 136.30, 140.00 (aryl carbons). 31P{1H} NMR (dichlo-  
romethane-d2): δ -2.86. 29Si NMR (dichloromethane-d2): δ  
250.6 br. At -80 °C: δ 259.4 (t, J SiP ) 34 Hz). IR: 1288 w,  
1013 w, 952 m, 938 m, 808 w, 740 m, 739 s, 730 s, 704 s, 603  
w. Equivalent conductance ) 31 Ω-1 cm2 equiv-1 (0.0037 M  
at 23 °C in dichloromethane). Mol wt in dichloromethane  
(isopiestic method): 990 (calcd 982 for ion pair).  
[Cp *(Me3P )2R u Si(SCy)2][BP h 4] (22). Dichloromethane  
(20 mL) was added to Cp*(Me3P)2RuSi(SCy)2Cl (0.41 g, 0.60  
mmol) and NaBPh4 (0.31 g, 0.90 mmol), and the resulting  
solution was stirred for 1.5 days. This yellow-orange solution  
was filtered to remove NaCl, and then all volatile components  
2
d2): δ 69.12 (t, J SiP ) 33 Hz). IR: 1294 w, 1274 w, 1111 w,  
1020 w, 955 s, 938 s, 845 w, 798 s, 712 m, 703 m, 665 m.  
Rea ction of Cp *(Me3P )2Ru Si(SMes)2Cl (7) w ith Me3Si-  
OTf. Me3SiOTf (8 µL, 0.04 mmol) was syringed into a  
benzene-d6 solution of 7 (0.03 g, 0.04 mmol), and the reaction  
was monitored by 1H and 31P NMR spectroscopy. After 8 h,  
two new products with spectroscopic characteristics consistent  
with Cp*(Me3P)2RuSi(SMes)Cl(OTf) (19) and Cp*(Me3P)2RuSi-  
(SMes)2OTf (18) were observed in a 2:1 ratio. NMR spectro-  
scopic data for 18 are as follows: 1H NMR (dichloromethane-  
d2): δ 1.50 (virtual t, 18 H, PMe3), 1.89 (s, 15 H, Cp*), 2.22 (s,  
3 H, SC6Me2H2Me), 2.36 (s, 6 H, SC6Me2H2Me), 6.82 (s, 4 H,  
SC6Me2H2Me). 31P{1H} NMR (benzene-d6): δ 3.48 (s).  
Cp *(Me3P )2Ru Si(SMes)(OTf)Cl (19). Me3SiOTf (0.11 mL,  
1.5 mmol) was added to a dichloromethane (5 mL) solution of  
7 (0.22 g, 0.75 mmol), and the resulting solution was stirred  
for 1 h. After the volatile materials were removed in vacuo,  
the resulting solid was washed with pentane (3 × 20 mL) and  
the product was crystallized from a 1:1 dichloromethane/  
diethyl ether mixture at -10 °C. Yield: 49% (0.11 g). Anal.  
Calcd for C26H44ClF3O3P2RuS2Si: C, 41.5; H, 5.90; Cl, 4.71.  
Found: C, 41.6; H, 5.90; Cl, 5.10. 1H NMR (benzene-d6): δ  
1.24 (virtual t, 18 H, PMe3), 1.70 (s, 15 H, C5Me5), 2.12 (s, 3  
H, SC6Me2H2Me), 2.82 (s, 6 H, SC6Me2H2Me), 6.95 (s, 4 H, SC6-  
Me2H2Me). 31P{1H} NMR (benzene-d6): δ 0.52 (d, J PP ) 39  
Hz, 1 P, PMe3), 2.06 (d, J PP ) 39 Hz, 1 P, PMe3). IR: 1362 s  
ν(SO3), 1233 m, 1208 s, 1189 s, 1146 m, 950 br s, 850 w, 715  
w, 619 m, 488 m, 418 m.  
[Cp *(Me3P )2Ru Si(SEt)2][BP h 4] (20). Compound 20 was  
prepared from 8 in 48% yield by the method used to obtain  
21. Anal. Calcd for C44H63BP2RuS2Si: C, 61.6; H, 7.40; Cl,  
0.00. Found: C, 61.7; H, 7.11; Cl, 0.12. 1H NMR (dichlo-  
romethane-d2): δ 1.45 (t, J ) 8 Hz, 6 H, SCH2CH3), 1.54  
(virtual t, 18 H, PMe3), 1.85 (s, 15 H, C5Me5), 3.14 (q, J ) 8  
Hz, 4 H, SCH2CH3), 6.88 (t, J ) 7 Hz, 4 H, BPh), 7.04 (t, J )  
7 Hz, 8 H, BPh), 7.32 (br s, 8 H, BPh). 13C{1H} NMR  
(dichloromethane-d2): δ 11.01 (C5Me5), 18.80 (SCH2CH3), 20.88  
(t, J CP ) 15 Hz, PMe3), 30.45 (SCH2CH3), 93.17 (C5Me5),  
122.07, 126.00, 136.26 (BPh4). 31P{1H} NMR (dichloromethane-  
d2): δ -2.22. 29Si NMR (-60 °C, dichloromethane-d2): δ 264.4  
br. IR: 1577 w, 1422 w, 1288 w, 1252 m, 1192 m, 1148 w,  
were removed in vacuo. Yield: 95%. Anal. Calcd for C50H28  
-
BP2RuS2Si: C, 63.7; H, 8.02. Found: C, 63.6; H, 7.65. Mp:  
89-96 °C, dec. 1H NMR (dichloromethane-d2): δ 1.4-1.8 (m,  
16 H, Cy) 1.55 (vir t, 18 H, PMe3), 1.86 (s, 15 H, C5Me5), 2.04  
(br m, 4 H, Cy), 3.63 (br m, 2 H, Cy), 6.88 (t, J ) 8 Hz, 4 H,  
BPh4), 7.04 (t, J ) 8 Hz, 8 H, BPh4), 7.32 (br m, 4 H, BPh4).  
13C{1H} NMR (dichloromethane-d2): δ 11.48 (C5Me5), 24.35 (vir  
t, PMe3), 25.40, 26.64, 37.05, 48.32 (Cy carbons), 95.84 (C5-  
Me5), 122.03, 125.94, 136.21, 164.38 (q, J CB ) 49 Hz, ipso  
carbon of BPh4). 31P{1H} NMR (dichloromethane-d2): δ -2.47.  
2
29Si NMR (dichloromethane-d2): δ 268.67 (t, J SiP ) 35 Hz).  
IR: 1577 w, 1284 w, 1258 m, 1022 br m, 952 s, 938 s, 848 w,  
800 w, 730 s, 701 s, 679 w, 610 m, 598 w, 561 m, 528 m.  
[Cp *(Me3P )2Ru Si(S-2-Na p h )2][B(C6F 6)3(S-2-Na p h )] (23).  
B(C6F6)3 (0.075 g, 0.15 mmol) and 4 (0.12 g, 0.13 mmol) were  
combined in an NMR tube with 0.7 mL of dichloromethane-  
d2, and the tube was shaken to dissolve the contents. After  
1
20 min, H, 13C, 29Si, and 31P NMR spectroscopy revealed the  
formation of a single product (23). Afterward, n-butyl ether  
was added to the sample, and upon concentrating the solution,  
crystals formed (0.080 g). These crystals were analyzed (by  
1H and 31P NMR spectroscopy and elemental analysis) as the  
starting material 4. Data for 23. 1H NMR (dichloromethane-  
d2): δ 1.37 (vir t, 18 H, PMe3), 1.91 (t, J HP ) 1 Hz, 15 H, C5-  
Me5), 7.22-7.75 (m, 21 H, Naph). 13C{1H} NMR (dichlo-  
romethane-d2): δ 11.47 (C5Me5), 23.92 (vir t, PMe3), 96.95  
(C5Me5), 124.22, 125.68, 126.29, 126.67, 127.52, 127.55, 127.64,  
128.05, 129.44, 129.54, 130.84, 130.93, 131.81, 133.08, 133.78,  
133.83, 134.05 (Naph aryl carbons), 136.95 (d of mult, J CF  
)
235 Hz, (S-2-Naph)B(C6F5)3), 138.85 (d of mult, J CF ) 253 Hz,  
(S-2-Naph)B(C6F5)3), 184.43 (d of mult, J CF ) 245 Hz, (S-2-  
Naph)B(C6F5)3). 31P{1H} NMR (dichloromethane-d2): δ -2.65.  
29Si{1H} NMR (dichloromethane-d2): δ 260.51 (t, J SiP ) 33 Hz).  
[Cp *(Me3P )2Ru dSiMe2][B(C6F 5)4] (24). LiB(C6F5)4‚Et2O  
(0.12 g, 0.16 mmol) and Cp*(Me3P)2RuSiMe2OTf (0.090 g, 0.15  
mmol) were combined in an NMR tube, which was then cooled  
to -78 °C. Dichloromethane-d2 (0.6 mL) was then added, and  
the tube was shaken to mix the reagents. The tube was  
warmed to 0 °C, and NMR spectra at this temperature  
5618 Organometallics, Vol. 17, No. 26, 1998  
Grumbine et al.  
indicated 90% conversion to one ruthenium product. X-ray  
quality crystals were grown by addition of a nBu2O solution  
(0.5 mL) of LiB(C6F5)4‚Et2O (0.050 g, 0.066 mmol) to a  
dichlorobenzene solution (1 mL) of Cp*(Me3P)2RuSiMe2OTf  
(0.040 g, 0.066 mmol) at 23 °C. Over the course of 5 min,  
nBu2O (2.5 mL) was added slowly until crystals began to form.  
The solution was left undisturbed for 18 h before the crystals  
were isolated by filtration. Yield: 0.028 g/38%. Anal. Calcd  
for C42H39BF20P2RuSi: C, 44.8; H, 3.49. Found: C, 44.7; H,  
3.42. 1H NMR (0 °C, dichloromethane-d2): δ 0.99 (s, 6 H,  
53.3; H, 8.34. 1H NMR (dichloromethane-d2): δ 0.30 (s, 6 H,  
SiMe2), 1.40 (virtual t, 18 H, PMe3), 1.60 (s, 15 H, C5Me5),  
7.05-7.21 (m, 3 H, Ph), 7.54 (m, 2 H, Ph). 13C{1H} NMR  
(dichloromethane-d2): δ 10.41 (SiMe2), 11.84 (C5Me5), 24.04  
(virtual t, PMe3), 93.13 (C5Me5), 125.48, 126.50, 134.99, 154.95  
(aryl carbons). 31P{1H} NMR (dichloromethane-d2): δ 6.48.  
29Si{1H} NMR (dichloromethane-d2): δ 18.91 (t, J SiP ) 28 Hz).  
Obser va tion of [Cp *(Me3P )2Ru SiMe2(P Me3)][B(C6F 5)4]  
(28). A solid mixture of Cp*(Me3P)2RuSiMe2OTf (0.012 g,  
0.020 mmol) and (Et2O)LiB(C6F5)4 (0.014 g, 0.020 mmol) was  
dissolved in 0.5 mL of dichloromethane-d2 to generate the  
silylene complex 24. The solution was then transferred to an  
NMR tube, which was sealed with a rubber septum. After  
cooling the tube to 0 °C, PMe3 (3.1 µL, 0.030 mmol) was added  
via syringe, generating a yellow solution of 28. 1H NMR  
SiMe2), 1.44 (vir t, 18 H, PMe3), 1.81 (t, J HP ) 1 Hz, 15 H,  
29  
C5Me5). 31P{1H} NMR (0 °C, dichloromethane-d2): δ 2.29.  
Si{1H} NMR (0 °C, dichloromethane-d2): δ 311.41 (br s).  
-
X-r a y Cr ysta l Deter m in a tion for 24. A yellow, blocklike  
crystal with approximate dimensions of 0.30 × 0.34 × 0.34  
mm was mounted in a glass capillary. The mounted crystal  
was placed under a cold stream of nitrogen on a Siemens P4  
diffractometer. Crystal quality was evaluated via measure-  
ment of intensities and inspection of peak scans. Automatic  
peak search and indexing procedures yielded a monoclinic  
reduced primitive cell. The 8444 raw intensity data were  
converted to structure factor amplitudes and their esd’s by  
correction for scan speed, background, and Lorentz and  
polarization effects. Inspection of the systematic absences  
indicated uniquely space group P21/n. Removal of systemati-  
cally absent and redundant data left 8128 unique data in the  
final data set. The structure was solved by direct methods  
and refined via standard least-squares and Fourier techniques.  
The maximum and minimum peaks on the final difference  
Fourier map corresponded to 0.80 and -0.52 e Å-3. The final  
residuals for 604 variables refined against the 4112 data were  
R ) 5.78%, Rw ) 7.46%, and GOF ) 1.31.  
[Cp *(Me3P )2Ru dSiP h 2][B(C6F 5)4]‚0.1CH2Cl2 (25). LiB-  
(C6F5)4‚Et2O (0.13 g, 0.16 mmol) and Cp*(Me3P)2RuSiPh2OTf  
(0.12 g, 0.15 mmol) were combined in an NMR tube, which  
was then cooled to -78 °C. Dichloromethane-d2 (0.6 mL) was  
then added, and the tube was shaken to give an orange-red  
solution. The tube was warmed to -30 °C, and NMR spectra  
at this temperature revealed the presence of only one product.  
After acquiring a 29Si NMR spectrum (-30 °C), the tube was  
cooled to -78 °C for 16 h to give orange-red crystals. The  
solvent was syringed out of the tube, and the tube was warmed  
to 23 °C. Under vacuum, the crystals desolvated and turned  
opaque. Yield: 0.042 g/22%. Anal. Calcd for C52H43BF20P2-  
RuSi‚(0.1CH2Cl2: C, 49.7; H, 3.46; Cl, 0.53. Found: C, 49.1;  
H, 3.42; Cl, 0.4. 1H NMR (-30 °C, dichloromethane-d2): δ 1.50  
(br s, 18 H, PMe3), 1.91 (br s, 15 H, C5Me5), 7.53 (br s, 10 H,  
SiPh2). 13C{1H} NMR (-30 °C, dichloromethane-d2): δ 10.91  
(C5Me5), 22.70 (vir t, PMe3), 95.22 (C5Me5), 127.52, 131.02,  
133.38, 147.05 (aryl carbons). 31P{1H} NMR (-30 °C, dichlo-  
romethane-d2): δ 1.67. 29Si{1H} NMR (-30 °C, dichlo-  
romethane-d2): δ 299 (t, J SiP ) 32 Hz).  
3
(dichloromethane-d2): δ 0.52 (d, J HP ) 4.5 Hz, 6 H, SiMe),  
2
1.39 (vir t, 18 H, PMe3), 1.42 (d, J HP ) 9.1 Hz, 9 H, PMe3),  
1.78 (s, 15 H, C5Me5). 31P{1H} NMR (dichloromethane-d2): δ  
-15.20 (s, 1 P), 2.87 (s, 2 P).  
Obser va tion of [Cp *(Me3P )2Ru SiMe2(P P h 3)][B(C6F 5)4]  
(29). A solution of 24 was generated in the same manner and  
on the same scale as described for 28. PPh3 (0.008 g, 0.030  
mmol) was added to the solution of 24, giving a dark yellow  
solution of 29. 1H NMR (dichloromethane-d2): δ 0.45 (d, 3J HP  
) 4.5 Hz, 6 H, SiMe), 1.30 (vir t, 18 H, PMe3), 1.79 (s, 15H,  
C5Me5), 7.34 (m, ArH), 7.65 (m, ArH). 31P{1H} NMR (dichlo-  
romethane-d2): δ 5.34 (s, 2 P), 21.53 (s, 1 P).  
[Cp *(Me3P )3Ru ][OTf]. To a solution of [Cp*Ru(NCCH3)3]-  
OTf (0.300 g, 0.590 mmol) in 20 mL of dichloromethane was  
added PMe3 (0.250 mL, 2.42 mmol) via syringe. After stirring  
this solution for 12 h, the volatile material was removed in  
vacuo and the residue was extracted with dichloromethane (2  
× 10 mL). Concentration of the solution to 10 mL, addition  
of 5 mL of diethyl ether, and cooling to -78 °C gave crystals  
of the product. Yield: 90% (0.326 g). Anal. Calcd for  
C20H42F3O3P3RuS: C, 39.15; H, 6.90. Found: C, 38.80; H, 7.15.  
Mp: 175-178 °C. 1H NMR (400 MHz, dichloromethane-d2):  
δ 1.46 (vir t, 27 H, PMe3), 1.76 (s, 15 H, C5Me5). 13C{1H} NMR  
(100 MHz, dichloromethane-d2): δ 12.10 (s, Cp*), 23.24 (m,  
PMe3), 96.36 (s, ring C5Me5). 31P{1H} NMR (121.5 MHz,  
dichloromethane-d2): δ 1.98 (s). IR (KBr pellet): 2977 s, 2915  
s, 1481 m, 1429 s, 1378 m, 1261 s, 1145 s, 1029 m, 962 s, 856  
m, 715 m, 669, m, 636 s, 570 w, 516 m.  
Obser va tion of [Cp *(Me3P )2Ru P P h 3][B(C6F 5)4] (31). A  
solution of 29 in dichloromethane-d2, as generated above, was  
allowed to stand at room temperature for 2 days. 1H and 31P  
NMR spectroscopy indicated nearly quantitative conversion  
to the product. 1H NMR (400 MHz, dichloromethane-d2): δ  
1.47 (m, 18 H, PMe3), 1.70 (s, 15 H, C5Me5), 7.45 (m, ArH),  
7.74 (m, ArH). 31P{1H} NMR (161.98 MHz, dichloromethane-  
2
2
d2): δ -4.88 (d, J PP ) 35 Hz, 2 P), 53.12 (t, J PP ) 35 Hz, 1  
P).  
Cp *(Me3P )2Ru Si[S(Tol-p)]2P h (26). PhMgBr (0.10 mL of  
a 3.2 M solution, 0.31 mmol) was syringed into a benzene (20  
mL) solution of Cp*(Me3P)2RuSi[S(Tol-p)]2OTf (0.25 g, 0.31  
mmol), and the resulting solution was stirred for 2 h while  
precipitation of MgBrOTf occurred. After the volatile material  
was removed in vacuo, the resulting residue was extracted  
with 2 × 20 mL of diethyl ether and the combined extracts  
were cooled to -35 °C to give a light yellow precipitate (0.041  
g). Yield: 18%. 1H NMR (dichloromethane-d2): δ 1.51 (virtual  
t, 18 H, PMe3), 1.77 (s, 15 H, Cp*), 2.09 (s, 6 H, SC6H4Me),  
6.52 (d, J ) 8 Hz, 4 H, SC6H4Me), 6.70 (d, J ) 8 Hz, 4 H,  
SC6H4Me), 6.98 (m, 3 H, Ph), 7.75 (m, 2 H, Ph). 13C{1H} NMR  
(dichloromethane-d2): δ 12.14 (C5Me5), 20.86 (SC6H4Me), 24.04  
(virtual t, PMe3), 94.77 (C5Me5), 126.09, 126.77, 128.38, 133.81,  
134.13, 135.36, 137.57, 144.67 (aryl carbons). 31P{1H} NMR  
(dichloromethane-d2): δ 3.24 (s).  
[Cp *(Me3P )2Ru SiMe2(CH2P P h 3)][B(C6F 5)4] (32a ). A 50  
mL round-bottom Schlenk flask was charged with Cp*(Me3P)2-  
RuSiMe2OTf (0.150 g, 0.252 mmol) and (Et2O)LiB(C6F5)4 (0.192  
g, 0.252 mmol). Dichloromethane (5 mL) was added after  
cooling the flask to 0 °C, and the mixture was stirred until all  
reactants dissolved. A cloudy yellow solution formed within  
30 s, indicating the formation of 24. The solution was then  
filtered into a precooled (0 °C) flask containing CH2PPh3 (0.070  
g, 0.253 mmol). The reaction mixture was stirred for 5 min,  
after which the volatile materials were removed under reduced  
pressure. The crude product was crystallized from 1:1 dichlo-  
romethane/diethyl ether (15 mL) at -78 °C. Yield: 80% (0.282  
g). Anal. Calcd for C61H56BF20P3RuSi: C, 52.26; H, 4.03.  
Found: C, 52.01; H, 3.67. Mp: 180-183 °C. 1H NMR (400  
MHz, dichloromethane-d2): δ -0.03 (s, 6 H, SiMe2), 1.27 (vir  
2
t, 18 H, PMe3), 1.84 (s, 15 H, C5Me5), 2.26 (d, J HP ) 16 Hz, 2  
Cp *(Me3P )2Ru SiMe2P h (27). This compound was pre-  
pared from 11 by the same method used for 26. Yield: 45%.  
Anal. Calcd for C24H44P2RuSi: C, 55.0; H, 8.47. Found: C,  
H, CH2), 7.68 (m, ArH), 7.78 (m, ArH). 13C{1H} NMR (100  
MHz, dichloromethane-d2): δ 1.26 (s, SiMe2), 15.25 (s, C5Me5),  
1
18.43 (d, J CP ) 36 Hz, PMe3), 41.41 (s, CH2), 114.78 (s, ring  
Ruthenium Silylene Complexes  
C5Me5), 113.10 (m, C6F5), 137.7 (dm, J CF ) 258 Hz, C6F5),  
Organometallics, Vol. 17, No. 26, 1998 5619  
1
(15 mL) was added, and the solution was cooled to -35 °C to  
give crystals of 35. A second crop was obtained upon addition  
of more diethyl ether and further cooling, to give a total yield  
of 0.225 g (24%). The filtrate was concentrated to 1 mL, and  
the volatile components of the mixture were vacuum trans-  
ferred and analyzed by 1H NMR and mass spectroscopy as  
consisting of primarily HSi(SEt)3. Anal. Calcd for C58H71BP2-  
RuSi2: C, 68.8; H, 7.17. Found: C, 68.1; H, 7.31. 1H NMR  
(dichloromethane-d2): δ -10.10 (t, J PH ) 9 Hz, 1 H, RuH), 1.31  
(vir t, 18 H, PMe3), 1.61 (s, 15 H, C5Me5), 3.77 (vir t, 2 H, SiH2-  
Ph3), 6.87 (t, J ) 7 Hz, 4 H, BPh4), 7.03 (t, J ) 7 Hz, 8 H,  
BPh4), 7.31 (br s, 8 H, BPh4), 7.42 (m, 9 H, SiH2Ph3), 7.59 (m,  
6 H, SiH2Ph3). 13C{1H} NMR (dichloromethane-d2): δ 10.69  
(C5Me5), 20.95 (vir t, PMe3), 99.65 (C5Me5), 122.07, 125.98,  
128.67, 130.14, 135.23, 136.26, 136.33 (aryl carbons), 164.33  
(q, J CB ) 49 Hz, ipso carbon of BPh4). 31P{1H} NMR (dichlo-  
romethane-d2): δ -0.34 (s).  
1
1
145.15 (dm, J CF ) 243 Hz, C6F5), 148.44 (dm, J CF ) 249 Hz,  
2
2
C6F5), 163.9 (dd, J CPcis ) 5.2 Hz, J CPtrans ) 49 Hz). 31P{1H}  
NMR (121.5 MHz, dichloromethane-d2): δ 5.85 (s, PMe3), 21.81  
(s, PPh3). 29Si{1H} NMR (dichloromethane-d2): δ 35.24 (td,  
2
2
J SiP ) 32 Hz, J SiP ) 15 Hz). IR: 1278 s, 1251 m, 1202 m,  
1095 w, 988 s, 791 m, 767 w, 743 m, 663 m, 585 m.  
[Cp *(Me3P )2Ru SiMe2(CH2P P h 3)]OTf (32b). CH2PPh3  
(0.070 g, 0.253 mmol) was dissolved in dichloromethane (5 mL),  
and the resulting solution was added via cannula to a solution  
of Cp*(Me3P)2RuSiMe2OTf (0.150 g, 0.252 mmol) in dichlo-  
romethane (5 mL). After stirring the reaction mixture for  
approximately 5 min, the volatile material was removed in  
vacuo to leave a bright yellow residue, which was crystallized  
from 1:1 dichloromethane/diethyl ether (15 mL) at -78 °C.  
Yield: 89% (0.196 g). Anal. Calcd for C38H56F3O3P3RuSSi: C,  
52.34; H, 6.47. Found: C, 52.04; H, 6.10. Mp: 129-133 °C.  
1
The H and 31P NMR spectra were identical to those for 32a .  
Rea ction of 20 w ith H3SiMes. Compound 8 (0.875 g, 1.27  
mmol) and NaBPh4 (0.800 g, 2.34 mmol) were stirred in  
dichloromethane (10 mL) for 5 h, and then the solution was  
filtered. H3SiMes (1 equiv) was syringed into the resulting  
solution, and stirring was continued for 4 days. The reaction  
solution was concentrated to 0.5 mL and was then extracted  
with pentane (2 × 4 mL) to leave a light yellow powder which  
was crystallized from dichloromethane/diethyl ether to give  
[Cp*(Me3P)2RuHCl][BPh4] (34). Addition of more diethyl ether  
and cooling (-35 °C) gave a second crop for a combined yield  
of 0.32 g (34%). The pentane extract from above was cooled  
to -35 °C, to give white crystals of BPh3 (0.075 g, 24% yield;  
IR: 1268 m, 1249 s, 1210 w, 1156 s, 1043 m, 943 w, 832 m,  
812 m, 774 m, 715 w, 686 w, 602 w, 593 w, 574 w.  
X-r a y Cr ysta l Deter m in a tion for 32b‚CH2Cl2. A yellow  
trapezoidal crystal with approximate dimensions of 0.15 × 0.20  
× 0.30 mm was mounted on a glass fiber using Paratone N  
hydrocarbon oil. The mounted crystal was placed under a cold  
stream of nitrogen on the diffractometer. Data were collected  
using a Siemens SMART diffractometer with a CCD area  
detector. A preliminary orientation matrix and unit cell  
parameters were determined by collecting 60 10-s frames. A  
hemisphere of data was collected at a temperature of -116 (  
1 °C using ω scans of 0.30° and a collection time of 20 s per  
frame. Frame data were integrated using SAINT. The data  
were corrected for Lorentz and polarization effects. No  
absorption correction was applied. The 9339 reflections that  
were integrated were averaged in point group 2/m to yield 3557  
unique reflections (Rint ) 0.032). No decay correction was  
necessary. The space group was determined to be P21 (No.  
4). The structure was solved using direct methods (SIR92)  
and refined by full-matrix least-squares methods using teXsan  
software. The non-hydrogen atoms were refined anisotropi-  
cally, while the hydrogen atoms were included at calculated  
positions but not refined. The number of variable parameters  
was 477, giving a data/parameter ratio of 7.25. The maximum  
and minimum peaks on the final difference Fourier map  
corresponded to 0.93 and -1.01 e-/Å3: R ) 0.041, Rw ) 0.050,  
GOF ) 2.75.  
Rea ction of 20 w ith H2 a n d Isola tion of [Cp *(Me3P )2-  
Ru H2][BP h 4] (33). Compound 8 (0.500 g, 0.727 mmol) and  
NaBPh4 (0.498 g, 1.46 mmol) were stirred in dichloromethane  
for 2 h, and then the solution was filtered. Hydrogen gas was  
bubbled into the resulting solution of [Cp*(Me3P)2RudSi(SEt)2]-  
[BPh4], the reaction flask was closed, and then the reaction  
mixture was stirred for 3.5 days. The volatile material was  
removed under reduced pressure to yield a light green oil. The  
oil was washed with pentane (3 × 10 mL), leaving a solid,  
which was purified by crystallizing from a 1:1 dichloromethane/  
diethyl ether mixture at -40 °C. Yield: 38% (0.198 g). Anal.  
Calcd for C40H55RuP2B: C, 67.70; H, 7.81. Found: C, 67.96;  
H, 7.48. Mp: 190 °C (dec). 1H NMR (dichloromethane-d2): δ  
-10.04 (t, J PH ) 33 Hz, 1 H, RuH), 1.51 (vir t, 18 H, PMe3),  
1.94 (s, 15 H, C5Me5), 6.96 (t, J ) 7 Hz, 4 H, BPh4), 7.11 (t, J  
) 7 Hz, 8 H, BPh4), 7.41 (br s, 8 H, BPh4). 13C{1H} NMR  
(dichloromethane-d2): δ 11.56 (C5Me5), 24.70 (m, PMe3), 100.33  
(C5Me5), 122.04, 125.94, 136.28, (aryl carbons), 164.33 (q, J CB  
) 49 Hz, ipso carbon of BPh4). 31P{1H} NMR (dichloromethane-  
d2): δ 10.10. IR (KBr pellet): 3052 s, 2996 s, 2910 m, 2138  
m, 1961 m, 1941 m, 1579 w, 1479 m, 1427 m, 1288 m. 1147  
w, 1068 w, 1029 m, 943 s, 854 m, 732 s, 703 s, 605 m.  
R ea ct ion of 20 w it h H 3SiSiP h 3 a n d Isola t ion of  
[Cp*(Me3P )2Ru H(SiH2SiP h 3)][BP h 4] (35). Complex 20 (0.796  
g, 0.928 mmol) and H3SiSiPh3 (0.282 g, 0.972 mmol) were  
stirred in dichloromethane (15 mL) for 7 days. Diethyl ether  
1
by H NMR spectroscopy). The pentane filtrate was concen-  
trated further to an oil, and then this residue was vacuum-  
transferred (10 h at 35 °C and 0.001 Torr). Analysis by 1H,  
13C, 29Si NMR and mass spectrometry revealed the presence  
of H3SiMes and the new product H2SiMes(SEt). The identity  
of the latter product was confirmed by an independent  
synthesis, involving reaction of H3SiMes with Ph3CCl to form  
H2SiMes(Cl), which was then reacted with LiSEt to form H2-  
SiMes(SEt).41 GC/MS (EI) parent ion: m/e 210. 1H NMR  
(dichloromethane-d2): δ 1.34 (t, J ) 8 Hz, 3 H, SCH2CH3), 2.34  
(s, 3 H, Mes), 2.60, (s, 6 H, Mes), 2.66 (q, J ) 8 Hz, 2 H, SCH2-  
CH3), 5.22 (s, 1 H, SiH), 6.95 (s, 2 H, Mes). 13C{1H} NMR  
(dichloromethane-d2): δ 18.18 (SCH2CH3), 21.40 (SCH2CH3),  
23.50 (Mes), 23.68 (Mes), 128.79, 141.10, 145.29 (aryl carbons).  
29Si{1H} NMR (dichloromethane-d2): δ -37.35 (s).  
[Cp *(Me3P )2Ru H(SiH2Mes)][BP h 4] (36). [Cp*(Me3P)2Ru-  
(NCMe)][BPh4] (0.020 g, 0.027 mmol) was combined with H3-  
SiMes (0.005 mL, 0.029 mmol) in dichloromethane-d2, and a  
small amount of new product was observed (8% by 1H and 31P  
NMR spectroscopy, 2 h) with spectroscopic characteristics  
consistent with 36. 1H NMR (dichloromethane-d2): δ -11.23  
(t, J PH ) 9 Hz, 1 H, RuH), 1.48 (vir t, 18 H, PMe3), 1.66 (s, 15  
H, C5Me5), 2.49 (s, 3 H, Mes), 2.49 (s, 6 H, Mes), 4.69 (t, J )  
8 Hz, 2 H, SiH2Mes). 31P{1H} NMR (dichloromethane-d2): δ  
-0.50. The silane HSi(SEt)3 was added to the reaction above  
(0.011 g, 0.060 mmol), and after 6 days the reaction mixture  
was found to contain H2SiMes(SEt) as the main SiH- and  
mesityl-containing product (90%, by 1H and 29Si NMR spec-  
troscopy).  
Ack n ow led gm en t is made to the National Science  
Foundation for their generous support of this work.  
Su p p or tin g In for m a tion Ava ila ble: Crystal, data col-  
lection, and refinement parameters, bond distances and angles,  
and anisotropic displacement parameters for 24 and 32b.CH2-  
Cl2 (21 pages). This material is contained in many libraries  
on microfiche, immediately follows this article in the microfilm  
version of the journal, can be ordered from ACS, and can be  
downloaded from the Internet; see any current masthead page  
for ordering information and Internet access instructions.  
OM980506E  

Products guided by the article

Product name:((CH3)5C5)Ru(P(CH3)3)2(Si(SC6H2(CH3)3)2(OSO2CF3))

Cas No:218140-19-3

218140-19-3

R&D Labs maybe for 218140-19-3

Relevant to this article

Hot Product