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JACS 1998 SN2 SN2 Pathway Example
JACS 1998 SN2 SN2 Pathway Example
Abstract: The titanocene sulfido complex Cp*2(py)TidS (1, py ) pyridine) reacts reversibly with terminal
alkynes to give the thiametallacyclobutenes Cp*2Ti(SC(R)dCH) (R ) H (2), Ph (3), Tol (4), TMS (5)).
Complex 1 also reacts with alkyl halides to give products derived from formal 1,2-addition across the titanium-
sulfur bond. Treatment of 1 with allyl halides results in the formation of Cp*2Ti(X)SCH2CHCH2 (X ) Cl
(10), F (16), Br (17), I (18)). Reaction of 1 with alkyl-substituted allyl chlorides showed that displacement of
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the halide anion occurs with SN2′ regiochemistry. A kinetic study of the conversion of 1 to 10 is consistent
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with a mechanism in which pyridine dissociation from the metal center precedes reaction of allyl chloride
with the Cp*2TidS fragment. The SN2′ regiochemistry of the reaction is explained by postulating coordination
of the halogen atom to the metal center in the reaction transition state. Complex 1 also reacts with allyl
tosylate, but labeling experiments show (in contrast to the allyl chloride reaction) that substitution of the tosylate
functionality occurs via a SN2 pathway. Heterocycles formed from the reaction of 1 with R,β-unsaturated
aldehydes were also isolated and characterized.
Introduction Scheme 1
In contrast to the inertness of many transition metal multiple
bonds,1 the MdX (X ) O, NR, S, PR) linkage in titanocene
and zirconocene complexes is unusually reactive. A wide range
of transformations has now been established for these com-
plexes, including overall [2 + 2] cycloadditions with olefins,2,3
alkynes,4-7 imines,8 and carbonyls9 and C-H10 and H-H11 bond
cleavage reactions with hydrocarbons and dihydrogen.12
In an attempt to extend this chemistry to titanium-sulfur
multiple bonds, we recently synthesized Cp*2(py)TidS (1, Cp*
) η5-C5Me5) and studied its reactivity toward dihydrogen and
silanes.13 We have now found that the TidS bond in 1 exhibits Results
cycloaddition reactivity, and in this paper we report the Reactions of 1 with Terminal Alkynes and Nitriles.
regioselective reactions of 1 with alkynes and nitriles. In Although no reaction occurs when 1 is treated with dipheny-
addition, we have investigated the nucleophilicity of 1 and have lacetylene, the sulfido complex reacts with terminal alkynes at
found that this complex undergoes an especially regioselective room temperature over a period of several hours to give the
series of SN2′ substitution reactions with allyl chlorides. orange thiametallacyclobutenes 2-5 (Scheme 1) in good yield.
(1) Nugent, W. A.; Mayer, J. M. Metal-Ligand Multiple Bonds; John In all cases the 1H NMR spectrum of the product shows only
Wiley and Sons: New York, 1988. one Cp* resonance, suggesting that a single regioisomer has
(2) Walsh, P. J.; Hollander, F. J.; Bergman, R. G. Organometallics 1993, been formed in the reaction. Attempts to determine the regio-
12, 3705.
(3) Schwartz, D. J.; Smith, M. R.; Andersen, R. A. Organometallics 1996, chemistry of the cycloaddition by hydrolysis of the metallacycle
15, 1446. to the corresponding ketones with dilute aqueous HCl5 led to
(4) Walsh, P. J.; Baranger, A. M.; Bergman, R. G. J. Am. Chem. Soc. the formation of several products (as determined by GC
1992, 114, 1708.
(5) Baranger, A. M.; Walsh, P. J.; Bergman, R. G. J. Am. Chem. Soc.
analysis). However, the large downfield shifts of the alkynyl
1993, 115, 2753. protons in the 1H NMR spectra of 2-5 (to between 8.5 and 7.8
(6) Lee, S.; Bergman, R. G. Tetrahedron 1995, 51, 4255. ppm) and the appearance of methine carbon resonances between
(7) Carney, M. J.; Walsh, P. J.; Hollander, F. J.; Bergman, R. G. 220 and 190 ppm in the 13C{1H} NMR spectra of these products
Organometallics 1992, 11, 761.
(8) Meyer, K. E.; Walsh, P. J.; Bergman, R. G. J. Am. Chem. Soc. 1995, are consistent with formation of thiametallacyclobutene com-
117, 974. pounds in which the terminal methine carbon is bound to
(9) Lee, S. Y.; Bergman, R. G. J. Am. Chem. Soc. 1996, 118, 6396. titanium.
(10) Lee, S. Y.; Bergman, R. G. J. Am. Chem. Soc. 1995, 117, 5877.
(11) Howard, W. A.; Trnka, T. M.; Waters, M.; Parkin, G. J. Organomet. To further confirm the regiochemistry of these cycloadditions,
Chem. 1997, 528, 95. a single-crystal X-ray diffraction study of 5 was performed.
(12) For leading references to reactive early-metal nonmetallocene imido Crystal and data collection parameters are shown in Table 1,
complexes see: Bennett, J.; Wolczanski, P. J. Am. Chem. Soc. 1997, 119, and details of the structure determination are given in the
10696.
(13) Sweeney, Z. K.; Polse, J. L.; Andersen, R. A.; Bergman, R. G.; Experimental Section and as Supporting Information. An
Kubinec, M. G. J. Am. Chem. Soc. 1997, 119, 4543. ORTEP diagram of 5 is presented in Figure 1, and selected bond
S0002-7863(98)00877-4 CCC: $15.00 © 1998 American Chemical Society
Published on Web 07/23/1998
7826 J. Am. Chem. Soc., Vol. 120, No. 31, 1998 Sweeney et al.
Scheme 2
Scheme 3
Scheme 4
Scheme 6
Scheme 7
Scheme 9 k3k4[RCl][1]
rate ) ) kobs[1] (5)
k-3[py] + k4[RCl]
1 1
) +
kobs k3 ( )( )
k-3 [py]
k3k4 [RCl]
(6)
Experimental Section
General Methods. Unless otherwise noted, all reactions and
manipulations were carried out in dry glassware under a nitrogen or
argon atmosphere using standard Schlenk techniques or at 20 °C in a
Vacuum atmospheres 553-2 drybox equipped with a MO-40-2 inert
gas purifier. The amount of O2 in the drybox atmosphere was
Figure 7. Postulated transition states for the reaction of 1 with allyl monitored with a Teledyne model no. 316 trace oxygen analyzer. Some
chlorides (A) and R,β-unsaturated aldehydes (B). reactions were carried out in thick-walled glass vessels fused to vacuum
stopcocks. These vessels are referred to in the procedures as bombs.
consistent with the observed pyridine inhibition of the reaction The other instrumentation and general procedures used have been
described previously.53
rate, since pyridine dissociation must precede interaction of the
Unless otherwise specified, all reagents were purchased from
halide with the metal center. It should be noted that Parkin et commercial suppliers and used without further purification. Pyridine
al. have recently suggested that the deprotonation of acetone was distilled sequentially from CaH2 and sodium and was stored over
and tBuI by Cp*2Zr(O)py may occur via similar transition activated 4 Å molecular sieves. Sulfur was dissolved in dry benzene
states.11 containing activated 4 Å molecular sieves, stirred overnight, and then
This hypothesis also explains the different substitution recrystallized from the filtered benzene solution. Pentane and hexane
regioselectivity (SN2 rather than SN2′) observed when 1 reacts (UV grade) were distilled from sodium benzophenone ketyl/tetraglyme
with allyl tosylate. Apparently, the tosylate moiety is unable under nitrogen. Deuterated solvents for NMR experiments were dried
to interact directly with the metal center in a transition state in the same way as their protiated analogues but were vacuum
transferred from the drying agent. Acetylene was bubbled through
leading to SN2′ substitution, and so the lowest energy reaction
concentrated H2SO4 and passed through two -78 °C cold traps. Methyl
pathway involves direct attack on the substituted carbon. The iodide, phenylacetylene, tolylacetylene, nitriles, R,β-unsaturated alde-
observation that the reaction of 1 with allyl tosylate is hydes, allyl fluoride, and all allyl chlorides were dried over activated
considerably slower than the reaction of 1 with allyl chloride, 4 Å molecular sieves before use. Cp*2Ti(C2H4) was prepared by the
even though tosylates are generally more easily displaced than literature method, except that Cp*2TiCl was used instead of Cp*2TiCl2.54
chlorides,50,51 provides further evidence that these reactions do 3-Chloro-3-methylbut-1-ene,55 allyl tosylate, and allyl tosylate-1-d56
not proceed via the same mechanism.52 were prepared according to literature procedures.
It is also possible that the reactions of 1 with R,β-unsaturated The HMQC experiment was recorded on a Brucker AMX spec-
trometer resonating at 300.13 MHz for 1H and 75.42 MHz for 13C that
aldehydes occur via six-membered transition states (Figure 7B).
was equipped with an inverse probe. One-dimensional NMR spectra
In this case, the carbonyl functionality would interact with the were recorded on the Brucker AMX spectrometer described above or
metal center through one of the oxygen lone pairs. However, on a Brucker AMX spectrometer resonating at 400 MHz for 1H and
attack of “soft” nucleophiles at the β position of R,β-unsaturated 100 MHz for 13C that was equipped with a QNP probe. 1H and 13C-
aldehydes is much more common than SN2′ substitution of allyl {1H} NMR spectra were referenced to resonances corresponding to
halides, so the postulate of a concerted reaction proceeding via residual protons or carbon atoms of the solvent. 19F NMR spectra were
a six-membered transition state may not be necessary to explain externally referenced to CCl3F (δ ) 0.0 ppm).
the regioselectivity observed in these transformations. Cp*2Ti(dS)py (1). A solution of Cp*2Ti(CH2CH2) (486 mg, 1.40
mmol) and pyridine (0.56 mL, 5 equiv) in toluene (20 mL) was cooled
to -40 °C. To this stirred solution, a suspension of freshly recrystal-
Conclusion
lized sulfur (33 mg, 1.0 equiv) in cold toluene was added dropwise.
We have shown that the (decamethylcyclopentadienyl)- The green solution immediately turned dark. After 40 h, the solvent
was reduced in vacuo (to approximately 10 mL) and pentane was
titanium sulfido complex 1 undergoes regiospecific cycloaddi-
layered onto the toluene solution. This mixture was cooled to -40 °C
tion reactions with nitriles and terminal alkynes. These to yield 1 as red crystals (459 mg, 76%). 1H NMR (C6D6): δ 8.00 (d,
transformations are probably mediated by the vacant metal 2H), 6.64 (m, 1H), 6.25 (m, 2H), 1.90 (s, 30H) ppm. 13C NMR: δ
orbital adjacent to the sulfido ligand in the 16-electron Cp*2- 135.9 (CH), 128.3 (CH), 122.4 (CH), 120.3 (C-CH3), 13.3 (C-CH3)
TidS species. We have also found that 1 undergoes very ppm. IR (Nujol): 2730, 1598, 1209, 1014, 802, 755, 709 cm-1. MS
regioselective nucleophilic substitution reactions with alkyl (EI): m/z 430 (M+). Anal. Calcd for C25H35NSTi: C, 69.90; H, 8.22;
halides, alkyl tosylates, and R,β-unsaturated aldehydes. A N, 3.26. Found: C, 69.88; H, 8.25; N, 3.23.
kinetic study has established that the reaction of 1 with allyl Cp*2Ti(SC(H)CH) (2). A bomb was charged with 1 (95 mg, 0.22
chlorides involves initial reversible dissociation of pyridine. This mmol) dissolved in benzene (10 mL). Acetylene was bubbled through
is most likely followed by coordination of the halogen atom at the solution for 5 min, and the resulting mixture was allowed to stand
overnight. The solution was filtered several times through fiberglass
the metal center and attack of the sulfur atom at the γ-carbon,
filter paper, and the volatile materials were removed in vacuo.
leading to product via a six-membered transition state. In this Crystallization of the residue from a toluene/hexane solution at -40
way the vacant metal-based orbital also plays an important role °C gave 52 mg (62%) of 2 as brown crystals. 1H NMR (C6D6): δ
in substitution reactions of these metal-heteroatom complexes. 7.42 (d, J ) 9.9 Hz, 1H), 6.95 (d, J ) 9.9 Hz, 1H), 1.69 (s, 30H) ppm.
13C NMR: δ 194.9 (CH), 120.0 (C-CH ), 96.5 (CH), 11.8 (C-CH )
3 3
(50) March, J. AdVanced Organic Chemistry, 4th ed.; John Wiley & ppm. IR (Nujol): 2723, 1490, 1446, 1187, 1020, 806, 673 cm-1. MS
Sons: New York, 1992.
(51) Streitwieser, A. SolVolytic Displacement Reactions; McGraw-Hill: (EI): m/z 376 (M+). Anal. Calcd for C22H32STi: C, 70.20; H, 8.57.
New York, 1962. Found: C, 70.10; H, 8.67.
(52) The relative rates of the reactions of 1 with benzyl chloride and Cp*2Ti(SC(Ph)CH) (3). A Schlenk flask equipped with a Teflon
allyl tosylate suggest that benzyl chloride substitution also does not occur stir bar was charged with 1 (51 mg, 0.12 mmol) dissolved in benzene
via a simple SN2 mechanism. The rate of this reaction is inhibited by
pyridine, indicating that halide dissociation might be assisted by coordination (53) Meyer, K. E.; Walsh, P. J.; Bergman, R. G. J. Am. Chem. Soc. 1995,
of the halide to the metal center in the transition state of the substitution. 117, 3749.
It is possible that formation of 9 occurs via Claisen-type attack of sulfur at (54) Cohen, S. A.; Auburn, P. R.; Bercaw, J. E. J. Am. Chem. Soc. 1983,
the ortho position of the aromatic ring, followed by 1,3-migration to give 105, 1136.
the observed product. At this time we are unable to distinguish between (55) Sneen, R. A.; Key, P. S. J. Am. Chem. Soc. 1972, 94, 6983.
this mechanism or other processes such as those proceeding via electron (56) Baldwin, J. E.; Bradley, M.; Turner, N. J.; Adlington, R. M.; Pitt,
transfer. A. R.; Sheridan, H. Tetrahedron 1991, 47, 8203.
7832 J. Am. Chem. Soc., Vol. 120, No. 31, 1998 Sweeney et al.
(5 mL). Phenylacetylene (80 µL, 0.72 mmol) was dissolved in benzene was crystallized from toluene at -40 °C to yield 87 mg of 9 (78%) as
(2 mL), and the solutions were combined. The reaction mixture was blue crystals.1H NMR (C6D6): δ 7.48 (m, 2H), 7.01 (m, 3H), 4.32 (s,
stirred overnight, and the volatile materials were removed to yield 52.1 2H), 1.88 (s, 30H) ppm. 13C NMR: δ 144.8 (CH), 129.2 (C), 128.7
mg of analytically pure 3 (95%). 1H NMR (C6D6): δ 8.06 (m, 2H), (CH), 126.0 (CH), 125.4 (C-CH3), 48.7 (CH2), 12.8 (C-CH3) ppm.
7.80 (s, 1H), 7.27 (m, 2H), 7.11 (m, 1H), 1.69 (s, 30H) ppm. 13C IR (Nujol): 3058, 2707, 1598, 1492, 1218, 1182, 1066, 1020, 707 cm-1.
NMR: δ 191.4 (CH), 137.5 (C), 128.2 (CH), 126.6 (CH), 126.4 (C- MS (EI) m/z 476 (M+) Anal. Calcd for C27H37ClSTi: C, 67.99; H,
CH3), 122.0 (CH), 115.3 (C), 12.1 (C-CH3) ppm. IR (Nujol): 3100, 7.82. Found: C, 67.89; 7.64.
2717, 1968, 1874, 1789, 1737, 1164, 1020, 904, 730 cm-1. MS (EI): Cp*2Ti(Cl)SCH2CHCH2 (10). A bomb containing a frozen solution
m/z 452 (M+). Anal. Calcd for C28H36STi: C, 74.32; H, 8.02. of 1 (164 mg, 0.38 mmol) in benzene was evacuated, and 1.5 equiv
Found: C, 74.35; H 8.02. (0.57 mmol) of 3-chloropropene was condensed onto the frozen solution
Cp*2Ti(SC(Tol)CH) (4). A scintillation vial was charged with 1 at -196 °C. Upon thawing, the solution color changed immediately
(122 mg, 0.28 mmol) in benzene (5 mL). p-Tolylacetylene (165 mg, from red to green. The solution was allowed to stand for 2 h, and the
1.4 mmol) was added via syringe, and the solution was stirred at RT volatile materials were removed. The resulting green solid was
(room temperature) for 2 d. The volatile materials were removed, and recrystallized from ether/pentane at -40 °C to yield 10 as purple crystals
the remaining solid was crystallized from a toluene/pentane mixture at (99 mg, 61%). 1H NMR (C6D6): δ 6.13 (m, 1H), 5.19 (m, 1H), 4.95
-40 °C to yield 4 as dark orange crystals (98 mg, 74%). 1H NMR (m, 1H), 3.76 (m, 2H), 1.88 (s, 30H) ppm. 13C NMR: δ 139.0 (CH),
(C6D6): δ 7.98 (d, 2H, J ) 8.0 Hz), 7.79 (s, 1H), 7.10 (d, 2H, J ) 8.0 125.3 (C-CH3, 113.3 (CH), 47.0 (CH2), 12.7 (C-CH3) ppm. IR
Hz), 1.80 (s, 3H), 1.70 (s, 30 H) ppm. 13C NMR: δ 190.3 (CH), 135.4 (Nujol): 3054, 2719, 1631, 1209, 1072, 1018, 917, 744 cm-1. MS
(C), 134.5 (C), 129.0 (CH), 126.3 (CH), 121.7 (C-CH3), 114.8 (CH), (EI): m/z 426 (M+). Anal. Calcd for C23H35ClSTi: C, 64.71; H, 8.26.
20.8 (CH3), 11.9 (C-CH3) ppm. IR (Nujol): 3020, 2713, 1565, 1506, Found: C, 64.74; H, 8.28.
1118, 1020, 817, 757, 636 cm-1. MS (EI): m/z 466 (M+). Anal. Calcd Cp*2Ti(Cl)SCH2CHCHCH3 (11). A bomb containing a frozen
for C29H38STi: C, 74.66; H, 8.21. Found: C, 74.31; H, 8.13. solution of 1 (151 mg, 0.35 mmol) in benzene was evacuated, and 1.1
Cp*2Ti(SC(SiMe3)CH) (5). A scintillation vial was charged with equiv (0.39 mmol) of 3-chloro-1-butene was condensed in at -196
a solution of 1 (110 mg, 0.26 mmol) in benzene (5 mL). (Trimeth- °C. Upon thawing, the solution color changed immediately from red
ylsilyl)acetylene (150 mg, 1.5 mmol) was added via syringe. The to green. The solution was allowed to stand for several hours. The
reaction mixture was allowed to stir for 3 d. The volatile materials volatile materials were removed to give a green solid that was
were removed, and crystallization of the residue from pentane at -40 crystallized from toluene/pentane at -40 °C to give 11 as a blue,
°C gave 5 as large orange crystals (98 mg, 85%) 1H NMR (C6D6): δ crystalline solid (120 mg, 77%). 1H NMR (C6D6): δ 5.77 (m, 1H),
8.20 (s, 1H), 1.66 (s, 30H), 0.47 (s, 9H) ppm. 13C NMR: δ 210.4 5.56 (m, 1H), 3.74 (m, 2H), 1.90 (s, 30H), 1.59 (d, J ) 6.4 Hz, 3H)
(CH), 118.9 (C-CH3), 97.6 (C), 12.4 (C-CH3), 1.2 (CH3) ppm. IR ppm. 13C NMR: δ 132.1 (CH), 125.2 (C-CH3), 124.2 (CH), 46.6
(cyclohexane): 3008, 1498, 1459, 1373, 1240, 831, 742 cm-1. MS (CH), 17.7 (CH3), 12.7 (C-CH3) ppm. IR (Nujol): 3067, 2719, 1195,
(EI): m/z 448 (M+). Anal. Calcd for C25H40SSiTi: C, 66.93; H, 8.99. 1020, 960, 809, 694 cm-1. MS (EI): m/z 440 (M+). Anal. Calcd for
Found: C, 66.88; H, 9.07. C24H37ClSTi: C, 65.37; H, 8.46. Found: C, 65.40; H, 8.63.
Cp*2Ti(SC(Ph)N) (6). A scintillation vial was charged with 1 (192 Cp*2Ti(Cl)SCH(CH3)CHCH2 (12). A bomb containing a frozen
mg, 0.45 mmol) in benzene (5 mL). Benzonitrile (46 µL, 0.45 mmol) solution of 1 (151 mg, 0.27 mmol) in benzene was evacuated, and 1
was added via syringe. After 2 h, the volatile materials were removed equiv of crotyl chloride (0.27 mmol) was condensed into the bomb at
to give an orange solid that was recrystallized from toluene/pentane at -196 °C. Upon thawing, the solution color changed immediately from
-40 °C to yield 6 (132 mg, 65%) as orange crystals. 1H NMR red to green. The reaction mixture was allowed to stand for 2 h. The
(C6D6): δ 8.47 (m, 2H), 7.27 (t, 2H), 7.14 (m, 1 H), 1.72 (s, 30H) volatile materials were removed to yield a green solid that was
ppm. 13C NMR: δ 143.9 (C), 137.7 (C), 129.0 (CH), 128.3 (CH), crystallized from ether at -40 °C to yield 121 mg (77%) of 12 as blue
125.4 (CH), 123.1 (C-CH3), 11.8 (C-CH3) ppm. IR (Nujol): 3020, crystals. 1H NMR (C6D6): δ 6.45 (m, 1H), 5.31 (m, 1H), 5.08 (m,
2730, 2036, 1882, 1818, 1641, 1454, 1375, 1155, 1066, 881, 759, 692, 1H), 4.32 (m, 2H), 1.90 (s, 15H), 1.88 (s, 15H), 1.65 (d, J ) 6.8 Hz,
609 cm-1. MS (EI): m/z 454 (M + H+). Anal. Calcd for C27H35- 3H) ppm. 13C NMR: δ 144.4 (CH), 125.3 (C-CH3), 110.1 (CH2),
NSTi: C, 71.51; H, 7.78; N, 3.09. Found: C, 71.38; H, 7.84; N, 3.15. 48.1 (CH), 21.3 (CH3), 12.9 (C-CH3), 12.9 (C-CH3) ppm. IR
Cp*2Ti(SC(m-Tol)N) (7). A scintillation vial was charged with 1 (cyclohexane): 3087, 2732, 1635, 1498, 1378, 1029, 809, 727, 690
(103 mg, 0.24 mmol) in benzene (5 mL). m-Tolunitrile (29 uL, 0.24 cm-1. Anal. Calcd for C24H37ClSTi: C, 65.37; H, 8.46. Found: C,
mmol)) was added via syringe. After 6 h, the volatile materials were 65.60; H, 8.59.
removed to give an orange solid that was crystallized from toluene/ Cp*2Ti(Cl)SCH2CHC(CH3)2 (13). To a vial containing a stirred
pentane at -40 °C to yield 73 mg of 7 (56%) as an orange powder. 1H solution of 1 (186 mg, 0.43 mmol) in benzene was added 3-chloro-3-
NMR (C6D6): δ 8.52 (m, 1H), 7.34 (t, 1H), 7.15 (m, 1H), 6.97 (d, methylbut-1-ene (55 µL, 0.52 mmol) via syringe. The solution color
1H), 2.16 (s, 3H), 1.73 (s, 30H). 13C NMR: δ 143.9 (C), 137.8 (C), immediately changed from red to green. The solution was stirred for
137.4 (CH), 129.8 (CH), 128.8 (CH), 124.8 (CH), 123.0 (C-CH3), 30 min, and then the volatile materials were removed to give a green-
21.2 (CH3), 11.8 (C-CH3) ppm. IR (Nujol): 3045, 2719, 1795, 1619, blue solid that was recrystallized from ether at -40 °C to give 13 as
1020, 929, 784, 692, 559 cm-1. MS (EI): m/z 468 (M + 1). Anal. blue crystals (131 mg, 70%). 1H NMR (C6D6): δ 5.66 (m, 1H), 3.80
Calcd for C28H37NSTi: C, 71.93; H, 7.98; N, 3.00. Found: C, 71.80; (d, J ) 7.9 Hz, 2H), 1.90 (s, 30H), 1.70 (s, 3H), 1.66 (s, 3H). 13C
H, 7.86; N, 2.76. NMR: δ 131.3 (C), 126.4 (CH), 125.4 (C-CH3), 43.1 (CH2), 25.8
Cp*2Ti(I)SMe (8). A bomb was charged with 1 (135 mg, 0.31 (CH3), 18.2 (CH3), 13.0 (C-CH3) ppm. IR (Nujol): 3021, 2719, 1666,
mmol) in benzene (5 mL). Methyl iodide (0.35 mmol) was vacuum 1199, 1103, 1018, 848 cm-1. Anal. Calcd for C25H39ClSTi: C, 66.00;
transferred onto the frozen solution at -196 °C. The solution turned H, 8.64. Found: C, 65.83; H, 8.64.
green after standing for 5 min at RT. After 12 h, the volatile materials Cp*2Ti(Cl)SC(CH3)2CHCH2 (14). Neat 1-chloro-3-methyl-2-
were removed to yield a green solid. This material was crystallized butene (105 µL, 0.93 mmol) was added to a solution of 1 (100 mg,
from toluene/pentane at -40 °C to give 86 mg of 8 (55%) as a green 0.23 mmol) in C6H6 (5 mL). The reaction mixture was agitated and
solid. 1H NMR (C6D6): 2.89 (s, 3H), 1.94 (s, 30H) ppm. 13C NMR: then allowed to stand for 15 min. The volatile materials were removed,
δ 125.2 (C-CH3) 28.3 (CH3), 14.2 (C-CH3) ppm. IR (Nujol): 2721, and the remaining solid was crystallized from toluene/pentane at -40
1544, 1308, 1018, 582 cm-1. MS (EI) m/z 492 (M+). Anal. Calcd °C to yield 14 as large blue crystals (57 mg, 54%). 1H NMR (C6D6):
for C21H33ISTi: C, 51.23; H, 6.75. Found: C, 51.23; H, 6.76. δ 6.63 (m, 1H), 5.10 (m, 1H), 4.98 (m, 1H), 1.89 (s, 30H), 1.68 (s,
Cp*2Ti(Cl)SCH2Ph (9). Benzyl chloride (29 µL, 0.25 mmol) was 6H) ppm. 13C NMR: δ 151.4 (CH), 127.1 (C-CH3), 107.5 (CH2),
added via syringe to a stirred solution of 1 (100 mg, 0.23 mmol) in 55.5 (C), 33.1 (CH3), 13.4 (C-CH3) ppm. IR (Nujol): 2709, 1625,
benzene (5 mL). After 5 min the color of the solution had changed 1376, 1105, 1014, 904, 794, 694, 592 cm-1. MS (EI): m/z 454 (M+).
from red to purple. The reaction mixture was allowed to stir for 30 Anal. Calcd for C25H39ClSTi: C, 66.00; H, 8.64. Found: C, 65.91;
min, and the volatile materials were removed. The remaining solid H, 8.64.
Reactions of (η5-C5Me5)2(C5H5N)TidS J. Am. Chem. Soc., Vol. 120, No. 31, 1998 7833
Cp*2Ti(Cl)SCH(CHCH2)CHCH2 (15). 5-Chloro-1,3-pentadiene 1214, 1159, 1020, 846, 653 cm-1. MS (EI): m/z 434 (M+). Anal.
(30 µL, 0.27 mmol) was added to a solution of 1 (98 mg, 0.23 mmol) Calcd for C25H38OSTi: C, 69.11; H, 8.81. Found: C, 69.14; H, 8.79.
in benzene (7 mL). The reaction mixture was stirred for 4 h. The Cp*2TiSCH(Ph)C(CH3)CHO (21). A small scintillation vial was
volatile materials were removed, and the remaining solid was crystal- charged with a solution of 1 (148 mg, 0.36 mmol) in 5 mL of benzene.
lized from Et2O/pentane at -40 °C to yield 15 as a dark green solid R-Methyl-trans-cinnamaldehyde (72 µL, 0.52 mmol) was added via
(68 mg, 65%). 1H NMR (C6D6): δ 6.22 (m, 2H), 5.24 (m, 2H), 5.08 syringe, and the solution was agitated with a pipet. After 30 min, the
(m, 2H), 4.64 (m, 1H), 1.88 (s, 30H) ppm. 13C NMR: δ 140.5 (CH), volatile materials were removed, and the resulting green oil was
125.8 (C-CH3), 112.8 (CH2), 55.5 (CH), 13.15 (C-CH3) ppm. IR crystallized from pentane at -40 °C to give 70 mg of 21 (41%). 1H
(C6D6): 2983, 2718, 1631, 1525, 1390, 911, 773. Anal. Calcd for NMR (C6D6): δ 7.63 (m, 2H), 7.29 (s, 1H), 7.24 (t, 2H), 7.09 (t, 1H),
C25H37ClSTi: C, 66.30; H, 8.23. Found: C, 66.12; H, 8.32. 5.18 (s, 1H), 1.90 (s, 15H), 1.85 (s, 15H), 1.43 (s, 3H) ppm. 13C
Cp*2Ti(F)CH2CHCH2 (16). 3-Fluoropropene (0.63 mmol) was NMR: δ 158.3 (C(O)(H)), 146.6 (C), 129.5 (CH), 127.8 (CH), 126.7
condensed into a bomb containing a frozen benzene solution of 1 (90 (CH). 124.3 (C-CH3), 123.6 (C-CH3), 106.0 (C), 53.3 (CH), 17.5
mg, 0.21 mmol). The solution was thawed and was allowed to stand (CH3), 12.3 (C-CH3), 11.9 (C-CH3) ppm. IR (cyclohexane): 3064,
for 5 h. The volatile materials were removed to give a red solid that 3029, 2950, 2732, 1614, 1380, 1211, 1174, 709, 611 cm-1. MS (EI):
was crystallized from ether/pentane at -40 °C to give 16 as dark red m/z 496 (M+). Anal. Calcd for C30H40OSTi: C, 72.56; H, 8.12.
crystals (49 mg, 54%). 1H NMR (C6D6): δ 6.16 (m, 1H), 5.22 (m, Found: C, 72.68; H, 7.94.
1H), 4.98 (m, 1H), 3.52 (m, 2H), 1.84 (s, 30H) ppm. 13C NMR: δ X-ray Crystallographic Study of Cp*2Ti(SC(SiMe3)CHCH2) (5).
139.8 (CH), 124.1 (C-CH3), 112.6 (CH2), 41.9 (d, CH, JCF ) 7 Hz), Crystals of 5 suitable for X-ray diffraction were obtained by slow
11.7 (C-CH3) ppm. 19F NMR: δ 20.4 ppm. IR (Nujol): 3072, 2719, cooling of a pentane solution of 5 to -40 °C. A fragment of one of
1629, 1207, 1019, 907, 734 cm-1. Anal. Calcd for C23H35FSTi: C, these reddish lumps with the approximate dimensions of 0.15 × 0.20
67.30; H, 8.59. Found: C, 67.10; H, 8.58. × 0.27 mm was mounted on a glass fiber using Paratone N hydrocarbon
Cp*2Ti(Br)SCH2CHCH2 (17). 3-Bromopropene (26 µL, 0.29 oil. All measurements were made on a Siemens SMART diffractometer
mmol) was added via syringe to a vial containing a stirred solution of with a CCD area detector using graphite-monochromated Mo KR
1 (115 mg, 0.26 mmol) in benzene (5 mL). The solution color changed radiation. All calculations were performed using the TEXSAN
from red to green, and the solution was allowed to stir for 10 min. The crystallographic software package.
volatile materials were removed to give a blue-green solid that was Cell constants and an orientation matrix obtained from a least-squares
crystallized from ether/pentane at -40 °C to give 17 as dark blue refinement using the measured positions of 4907 reflections in the range
crystals (85 mg, 67%). 1H NMR (C6D6): δ 6.13 (m, 1H), 5.18 (m, 3.00 < 2θ < 45.00° corresponded to a primitive monoclinic cell with
1H), 4.95 (m, 1H), 3.82 (m, 2H), 1.91 (s, 30H) ppm. 13C NMR: δ dimensions given in the Supporting Information. The final cell
138.7 (CH), 125.4 (C-CH3), 113.4 (CH2), 48.2 (CH2), 13.1 (C-CH3) parameters and specific data collection parameters for this data set are
ppm. IR (Nujol): 3091, 2717, 1633, 1198, 1018, 908, 808, 732 cm-1. given in Table 1 or as Supporting Information. The systematic absences
Anal. Calcd for C23H35BrSTi: C, 58.61; H, 7.48. Found: C, 58.61; of h01, 1 * 2n, and 0k0, k * 2n, uniquely determined the space group
H, 7.70. to be P21/c (No. 14). Data were collected at a temperature of -100 (
Cp*2Ti(I)SCH2CHCH2 (18). 3-Iodopropene (18 µL 0.20 mmol) 1 °C.
was added via syringe to a vial containing a stirred solution of 1 (80 Data were integrated using SAINT with box parameters of 2.0 ×
mg, 0.19 mmol) in benzene (5 mL). The solution color changed from 2.0 × 0.6 deg to a maximum 2θ values of 51.7°. The data were
red to green, and the solution was allowed to stir for 10 min. The corrected for Lorentz and polarization effects. No decay correction
volatile materials were removed to give a blue-green solid that was was applied. An empirical absorption correction based on the measure-
crystallized from ether/pentane at -40 °C to give 18 as dark blue ment of redundant and equivalent reflections and an ellipsoidal model
crystals (71 mg, 73%). 1H NMR (C6D6): δ 6.15 (m, 1H), 5.18 (m, for the absorption surface was applied using XPREP (Tmax ) 0.90, Tmin
1H), 4.95 (m, 1H), 3.90 (m, 2H), 1.97 (s, 30H) ppm. 13C NMR: δ ) 0.83). The 11 074 integrated reflections were averaged to yield 4534
138.7 (CH), 125.4 (C-CH3), 113.9 (CH2), 49.6 (CH2), 14.2 (C-CH3) unique reflections (Rint ) 0.042). The structure was solved by direct
ppm. IR (Nujol): 3079, 2704, 1631, 1199, 1020, 908, 742, 594 cm-1. methods and expanded using Fourier techniques. All non-hydrogen
Anal. Calcd for C23H35ISTi: C, 53.29; H, 6.81. Found: C, 53.07; H, atoms were refined anisotropically. Hydrogen atoms were included at
6.81. calculated or in located positions but not refined. The final cycle of
Cp*2Ti(OSO2Tol)SCH2CHCH2 (19). Allyl tosylate (57 µL, 0.30 full matrix least-squares refinement was based on 2713 observed
mol) was added to a vial containing a stirred solution of 1 (119 mg, reflections (I > 3.00σ(I)) and 253 variable parameters and converged
0.28 mmol) in benzene (10 mL). The solution was stirred for 3 d at (largest parameter shift was 0.01 times its esd) with unweighted and
20 °C. The volatile materials were removed to give a brown oily solid weighted agreement factors of R ) 0.049 and Rw ) 0.056. The standard
that was washed with 5 mL of Et2O and pentane to give 19 as a brown deviation of an observation of unit weight was 1.89. The weighting
solid (87 mg, 56%). 1H NMR (C6D6): δ 7.97 (d, 2H, J ) 8.1 Hz), scheme was based on counting statistics and included a factor (p )
6.89 (d, 2H, J ) 8.0 Hz), 6.45 (m, 1H), 5.35 (m, 1H), 5.10 (m, 1H), 0.030) to downweight the intense reflections. The maximum and
4.72 (m, 2H), 1.96 (s, 3H), 1.90 (s, 30H) ppm. 13C NMR: δ 143.9 minimum peaks on the final difference Fourier map corresponded to
(C), 140.3 (C), 140.2 (CH), 128.8 (CH), 127.4 (C-CH3), 127.3 (CH), 0.77 and -0.55 e/Å3, respectively.
114.5 (CH2), 44.1 (CH2), 21.1 (CH3), 13.0 (C-CH3) ppm. IR (C6H6): X-ray Crystal Structure of Cp*2Ti(Cl)SC(CH3)2CHCH2 (14).
2900, 2829, 1783, 1670, 1396, 1164, 1058, 874, 858 cm-1. Anal. Calcd Green crystals of 14 suitable for X-ray diffraction were grown by slow
for C30H42S2O3Ti: C, 64.04; H, 7.52. Found: C, 64.28; H, 7.85. The cooling of a toluene/pentane solution of 14 to -40 °C. A block-shaped
2H NMR spectra of the 2H-substituted analogue (which was prepared
crystal having approximate dimensions of 0.10 × 0.11 × 0.17 mm
using 56 mg of 1 and the procedures described above) in C6H6 showed was mounted as described above. Data collection and calculations were
only a singlet at 4.7 ppm. The 13C{1H} spectrum of this compound also performed as described above. The specific data collection
was identical to that of the undeuterated analogue except the singlet at parameters are given in Table 1 or as Supporting Information. The
44 ppm was replaced by a 1:1:1 triplet. space group was determined to be P21/c (No. 14). Cell constants and
Cp*2TiSCH(CH3)C(CH3)CHO (20). trans-2-Butenal (50 mg, 0.52 an orientation matrix were obtained from 4509 reflections. Data were
mmol) was added via syringe to a stirred solution of 1 (150 mg, 0.35 integrated as described above using box parameters of 1.6 × 1.6 ×
mmol) in benzene. After 2 h the volatile materials were removed and 0.6 deg to a maximum 2θ value of 52.1°. The 11 366 integrated and
the remaining brown solid was crystallized from a toluene/pentane corrected reflections were averaged to yield 4378 unique data (Rint )
solution at -40 °C to give 128 mg of 20 (84%) as a purple solid. 1H 0.057). The final cycle of full-matrix least-squares refinement was
NMR (C6D6): δ 7.25 (s, 1H), 4.15 (q, J ) 6.3 Hz, 1H), 1.89 (s, 15H), based on 2416 observed reflections and converged (largest parameter
1.85 (s, 15H), 1.70 (d, J ) 6.3 Hz, 3 H), 1.67 (s, 3H) ppm. 13C NMR: shift was 0.45 times its esd) with unweighted and weighted agreement
δ 157.5 (CH), 122.0 (C-CH3), 43.2 (CH), 27.3 (CH3), 16.1 (CH3), factors of R ) 0.049 and Rw ) 0.055. The standard deviation of an
12.8 (C-CH3), 12.5 (C-CH3) ppm. IR (Nujol): 2723, 1687, 1612, observation of unit weight was 1.65 using the weighting scheme
7834 J. Am. Chem. Soc., Vol. 120, No. 31, 1998 Sweeney et al.
described above. The maximum and minimum peaks on the final 0.36 and -0.20 e/Å3. All non-hydrogen atoms were refined anisotro-
difference Fourier map corresponded to 0.36 and -0.36 e/Å3. All non- pically. Hydrogen atoms were included at calculated or in located
hydrogen atoms were refined anisotropically. Hydrogen atoms were positions but not refined.
included at calculated or in located positions but not refined.
X-ray Crystal Structure of Cp*2Ti(SCH(Ph)C(Me)CHO) (21). Acknowledgment. We thank the National Institutes of
Black crystals of 21 suitable for X-ray diffraction were grown by slow Health for generous financial support of this work (Grant No.
cooling of a toluene/pentane solution of 21 to -40 °C. A fragment of GM-25459 to R.G.B.), Dr. F. J. Hollander for solving the crystal
a block-shaped crystal having approximate dimensions of 0.16 × 0.18 structures of 5 and 21, Dr. Ryan Powers for solving the crystal
× 0.21 mm was mounted as described above. Data collection and structure of 14 (both at CHEXRAY, the U. C. Berkeley X-ray
calculations were performed as described for the X-ray analysis of 5.
diffraction facility), and a reviewer for a careful reading of the
The space group was determined to be P21/c (No. 14). The specific
data collection parameters are given in Table 1 or as Supporting manuscript.
Information. Cell constants and an orientation matrix were obtained
from 6064 reflections. Data were integrated as described above using Supporting Information Available: Tables giving details
box parameters of 1.8 × 1.8 × 0.6 deg to a maximum 2θ value of of the data collection, data reduction, and structure solution and
46.5 °. The 10 623 integrated and corrected reflections were averaged refinement, positional and thermal parameters, bond lengths,
to yield 3989 unique data (Rint ) 0.038). The final cycle of full-matrix bond angles, and torsion angles for 5, 14, and 21 and a table
least-squares refinement was based on 2635 observed reflections and and figure presenting data from the kinetic study of the reaction
converged (largest parameter shift was 0.02 times its esd) with between 1 and allyl chloride (22 pages, print/PDF). See any
unweighted and weighted agreement factors of R ) 0.033 and Rw ) current masthead page for ordering information and Web access
0.040. The standard deviation of an observation of unit weight was instructions.
1.47 using the weighting scheme described above. The maximum and
minimum peaks on the final difference Fourier map corresponded to JA980877M