Ruthenium-catalyzed homo and cross metathesis reactions of alkenylpolyboranes: New routes to functional o-carborane and decaborane derivatives

Article abstract of DOI:10.1021/om050851l

Both 1-(CH₂=CHCH₂)-1,2-C₂B ₁₀H₁₁ (1) and 6-[CH₂=CH(CH₂) ₄]-B₁₀H₁₃ (2) undergo homometathesis and cross metathesis reactions in the presence of the Cl₂Ru(=CHPh)(PCy ₃)L, L = PCy₃ (I) or H₂IMes (II), Grubbs catalysts. According to the Grubbs classification, 1 is a type-II olefin for I and a type-I olefin for II and 2 is a type-I olefin for both the I and II catalysts. Homometathesis of 1 produces the olefin-bridged compound 1,1′-(CH₂CH=CHCH₂)-(1,2-C₂B ₁₀H₁₁)₂ (3), while the cross metathesis reactions of 1 with a variety of olefins are efficient, high-yield routes to functional o-carborane 1-R-1,2-C₂B₁₀H₁₁ derivatives, including R = C₆H₅CH₂CH=CHCH ₂- (4), C₆H₅CH=CHCH₂- (5), CH ₃C(O)OCH₂CH= CHCH₂- (6), HOCH ₂CH=CHCH₂- (7), ClCH₂CH=CHCH₂- (8), C₆H₅CH₂OCH₂CH=CHCH₂- (9), CH₃(CH₂)₃CH=CHCH₂- (10), CF ₃C(O)OCH₂CH=CHCH₂- (11), CH₃C(O) (CH₂)₂CH=CHCH₂- (12), t-C₄H ₉OC(O)NHCH₂CH=CHCH₂- (13), NC(CH ₂)₃CH=CHCH₂- (14), and {[(CH₃) ₄C₂O₂]BCH₂CH= CHCH₂}- (15). Deboronation of 1,1′-(CH₂CH=CHCH₂)-(1,2-C ₂B₁₀H₁₁)₂ (3) with CsF affords the olefin-bridged bis(dicarbollide) salt 2Cs⁺·[7,7′- (CH₂CH=CHCH₂)-7,8-(C₂B₉H ₁₁)₂]^2- (16). Similar reactions of 1-[CH ₃(CH₂)₃CH=CHCH₂]-1,2-C ₂B₁₀H₁₁ (10) with CsF and tetrabutylammonium fluoride generate the Cs⁺ (17) and [N(C₄H ₉)₄]⁺ (18) [7-CH₃(CH ₂)₃CH=CHCH₂-7,8-C₂B ₉H₁₁]^- salts, respectively. Homometathesis of 2 affords 6,6′-[(CH₂)₄CH=CH(CH₂) ₄]-(B₁₀H₁₃)₂ (19), and its cross metathesis reactions with functional olefins yield a range of functionalized decaborane derivatives 6-R-B₁₀H₁₃ (R = C₆H ₅CH₂-CH=CH(CH₂)₄- (20), CH ₃C(O)OCH₂CH=CH(CH₂)₄- (21), C ₆H₅CH₂OCH₂CH==CH(CH ₂)₄- (22), ClCH₂CH=CH(CH₂) ₄- (23), CH₃(CH₂)₃CH=CH(CH ₂)₄- (24), CF₃C(O)OCH₂CH=CH(CH ₂)₄- (25), C₆H₅CH=CH(CH ₂)₄- (26), CH₃C(O)(CH₂) ₂CH=CH(CH₂)₄- (27), CH₃CH ₂OCH₂CH=CH(CH₂)₄- (28), and CH ₃OC(O)CH=CH(CH₂)₄- (29)). Cross metathesis of 1 with 2 produces 1-[1-(1,2-C₂B₁₀H₁₁)]-CH ₂-CH=CH(CH₂)₄-7-(6-B₁₀H ₁₃) (30), having o-carborane and decaborane cages linked by an alkenyl bridge.

Full text of DOI:10.1021/om050851l

Organometallics 2006, 25, 609-621
609
Ruthenium-Catalyzed Homo and Cross Metathesis Reactions of
Alkenylpolyboranes: New Routes to Functional o-Carborane and
Decaborane Derivatives
Xiaolan Wei, Patrick J. Carroll, and Larry G. Sneddon*
Department of Chemistry, UniVersity of PennsylVania, Philadelphia, PennsylVania 19104-6323
ReceiVed October 4, 2005
Both 1-(CH2dCHCH2)-1,2-C2B10H11 (1) and 6-[CH2dCH(CH2)4]-B10H13 (2) undergo homometathesis
and cross metathesis reactions in the presence of the Cl2Ru(dCHPh)(PCy3)L, L ) PCy3 (I) or H2IMes
(II), Grubbs catalysts. According to the Grubbs classification, 1 is a type-II olefin for I and a type-I
olefin for II and 2 is a type-I olefin for both the I and II catalysts. Homometathesis of 1 produces the
olefin-bridged compound 1,1′-(CH2CHdCHCH2)-(1,2-C2B10H11)2 (3), while the cross metathesis reactions
of 1 with a variety of olefins are efficient, high-yield routes to functional o-carborane 1-R-1,2-C2B10H11
derivatives, including R ) C6H5CH2CHdCHCH2- (4), C6H5CHdCHCH2- (5), CH3C(O)OCH2CHd
CHCH2- (6), HOCH2CHdCHCH2- (7), ClCH2CHdCHCH2- (8), C6H5CH2OCH2CHdCHCH2- (9),
CH3(CH2)3CHdCHCH2- (10), CF3C(O)OCH2CHdCHCH2- (11), CH3C(O)(CH2)2CHdCHCH2- (12),
t-C4H9OC(O)NHCH2CHdCHCH2- (13), NC(CH2)3CHdCHCH2- (14), and {[(CH3)4C2O2]BCH2CHd
CHCH2}- (15). Deboronation of 1,1′-(CH2CHdCHCH2)-(1,2-C2B10H11)2 (3) with CsF affords the olefin-
bridged bis(dicarbollide) salt 2Cs+‚[7,7′-(CH2CHdCHCH2)-7,8-(C2B9H11)2]2- (16). Similar reactions of
1-[CH3(CH2)3CHdCHCH2]-1,2-C2B10H11 (10) with CsF and tetrabutylammonium fluoride generate the
Cs+ (17) and [N(C4H9)4]+ (18) [7-CH3(CH2)3CHdCHCH2-7,8-C2B9H11]- salts, respectively. Homomet-
athesis of 2 affords 6,6′-[(CH2)4CHdCH(CH2)4]-(B10H13)2 (19), and its cross metathesis reactions with
functional olefins yield a range of functionalized decaborane derivatives 6-R-B10H13 (R ) C6H5CH2-
CHdCH(CH2)4- (20), CH3C(O)OCH2CHdCH(CH2)4- (21), C6H5CH2OCH2CHdCH(CH2)4- (22),
ClCH2CHdCH(CH2)4- (23), CH3(CH2)3CHdCH(CH2)4- (24), CF3C(O)OCH2CHdCH(CH2)4- (25),
C6H5CHdCH(CH2)4- (26), CH3C(O)(CH2)2CHdCH(CH2)4- (27), CH3CH2OCH2CHdCH(CH2)4- (28),
and CH3OC(O)CHdCH(CH2)4- (29)). Cross metathesis of 1 with 2 produces 1-[1-(1,2-C2B10H11)]-CH2-
CHdCH(CH2)4-7-(6-B10H13) (30), having o-carborane and decaborane cages linked by an alkenyl bridge.
caborane and 6-cyclooctenyldecaborane, to afford the corre-
sponding polyborane polymers.4 In this paper, we describe the
first use of these ruthenium carbene complexes to catalyze the
homo and cross metathesis reactions of alkenylpolyboranes and
demonstrate that these reactions provide efficient routes to a
wide range of functionalized alkenyl-o-carborane and alkenyl-
decaborane derivatives.
Introduction
Metal carbene catalyzed olefin metathesis reactions,1 employ-
ing either the early transition metal based “Schrock-type”
M(NAr)(dCHR)(OR′)2L, M ) Mo, W, catalysts2 or the late
transition metal based “Grubbs-type” Cl2Ru(dCHPh)(PCy3)L,
L ) PCy3 (I) and H2IMes (II), catalysts,3 provide facile, high-
yield routes to functional molecules and polymers. We previ-
ously reported the use of Grubbs ruthenium carbene complexes
to catalyze the ring-opening metathesis polymerization (ROMP)
reactions of alkenylpolyboranes, including 6-norbornenylde-
Experimental Section
General Synthetic Procedures and Materials. Unless otherwise
noted, all reactions and manipulations were performed in dry
glassware under nitrogen or argon atmospheres using the high-
vacuum or inert-atmosphere techniques described by Shriver.5
1-(CH2dCHCH2)-1,2-C2B10H11 (1)6a and 6-[CH2dCH(CH2)4]-
B10H13 (2)6b,c were prepared according to literature methods.
Allylbenzene, styrene, 1-hexene, methylacrylate, 2-allyl-4,4,5,5-
tetramethyl-1,3,2-dioxaboronate (allylpinacolborane), and allyl
chloride (Aldrich) were distilled prior to use. tert-Butyl-N-allyl-
(1) For general reviews of olefin metathesis, see: (a) Ivin, K. J.; Mol, J.
C. Olefin Metathesis and Metathesis Polymerization; Academic Press: San
Diego, 1997. (b) Grubbs, R. H. Handbook of Metathesis; Wiley-VCH:
Weinheim, John Wiley: Chichester, 2003. (c) Schuster, M.; Blechert, S.
Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-2056. (d) Connon, S. J.;
Blechert, S. Angew. Chem., Int. Ed. 2003, 42, 1900-1923. (e) Grubbs, R.
H. Tetrahedron 2004, 60, 7117-7140.
(2) (a) Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; Dimare,
M.; O’Regan, M. J. Am. Chem. Soc. 1990, 112, 3875-3886. (b) Bazan, G.
C.; Khosravi, E.; Schrock, R. R.; Feast, W. J.; Gibson, V. C.; O’Regan, M.
B.; Thomas, J. K.; Davis, W. M. J. Am. Chem. Soc. 1990, 112, 8378-
8387. (c) Bazan, G. C.; Oskam, J. H.; Cho, H. N.; Park, L. Y.; Schrock, R.
R. J. Am. Chem. Soc. 1991, 113, 6899-6907.
(4) Wei, X.; Carroll, P. J.; Sneddon, L. G. Organometallics 2004, 23,
163-165.
(5) Shriver, D. F.; Drezdzon, M. A. The Manipulation of Air-SensitiVe
Compounds, 2nd ed.; Wiley: New York, 1986.
(6) (a) Gomez, F. A.; Hawthorne, M. F. J. Org. Chem. 1992, 57, 1384-
1390. (b) Pender, M. J.; Wideman, T.; Carroll, P. J.; Sneddon, L. G. J. Am.
Chem. Soc. 1998, 120, 9108-9109. (c) Pender, M. J.; Carroll, P. J.; Sneddon,
L. G. J. Am. Chem. Soc. 2001, 123, 12222-12231.
(3) (a) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996,
118, 100-110. (b) Scholl, S.; Ding, S.; Lee, C. W.; Grubbs, R. H. Org.
Lett. 1999, 1, 953-956. (c) Sanford, M. S.; Love, J. A.; Grubbs, R. H. J.
Am. Chem. Soc. 2001, 123, 6543-6554. (d) Trnka, T. M.; Grubbs, R. H.
Acc. Chem. Res. 2001, 34, 18-29.
10.1021/om050851l CCC: $33.50 © 2006 American Chemical Society
Publication on Web 12/14/2005

610 Organometallics, Vol. 25, No. 3, 2006
Wei et al.
11
carbamate (Aldrich) was recrystallized from cold hexanes prior to
use. 2-Butene-1,4-diol, 1,4-cis-dibenzoxy-2-butene, cesium fluoride,
tetrabutylammonium fluoride (1 M solution in THF), trans-stilbene,
diacetoxybutene, Cl2Ru(dCHPh)(PCy3)L, L ) PCy3 (I) and H2-
IMes (II) (Aldrich), 5-hexen-2-one, allyltrifluoroacetate (Acros),
and ACS grade ethanol (Pharmaco) were used as received.
Allylethyl ether (Acros) and 5-cyano-1-pentene (Lancaster Syn-
thesis) were distilled prior to use. The 1-(CH2dCH)-1,2-C2B10H11
(KatChem) was sublimed prior to use. The 1,4-diphenyl-2-butene
was prepared according to literature methods.7 CH2Cl2 and THF
were purified by passage through an alumina column prior to use.
HPLC or ACS grade hexanes, benzene, ethyl acetate, and silica
gel with mesh sizes of 230-400 (Fisher) were used as received.
CDCl3 (D, 99.8%) and CD3OD (D, 99%) (Cambridge Isotope
Laboratory) were used as received. Thin-layer chromatography
(TLC) analyses were conducted on 0.5 mm silica gel F-254 plates
(Merck-5744) and stained with a basic KMnO4 solution to visualize
the carborane derivatives.
temperature. NCI-HRMS (m/e): calcd for 12C12
B
10
1H22 276.2652,
found 276.2652. Anal. Calcd: C, 52.52; H, 8.08. Found: C, 52.73;
H, 8.07. 11B NMR (160.1 MHz, CDCl3, ppm, J ) Hz): -4.4 (d,
1B, J 148), -7.7 (d, 1B, J 147), -11.1 (d, 2B, J 150), -13.0 (d,
1
2B, J 150), -14.6 (d, 2B, J 145), -15.0 (d, 2B, J 153). H NMR
(500.4 MHz, CDCl3, ppm, J ) Hz): 7.41-7.23 (m, 5H, C6H5),
5.78 (d of t of t, 1H, J1 15.1, J2 8.3, J3 1.1, dCH), 5.46 (d of t of
t, 1H, J1 15.2, J2 7.6, J3 1.5, dCH), 3.59 (s, br, 1H, cage C-H),
3.46 (d, 2H, J 6.8, dCH-CH2), 2.98 (d, 2H, J 7.5, dCH-CH2).
IR (NaCl plate, cm-1): 3060 (s), 2920 (w), 2600 (vs), 2320 (w),
1900 (br, w), 1450 (m), 1270 (w), 1255 (s), 1205 (w), 1110 (m),
1050 (m), 1010 (s), 970 (s), 930 (w), 755 (w), 720 (s), 690 (w).
1-(C6H5CHdCHCH2)-1,2-C2B10H11 (5). As described for 3,
0.27 g (1.5 mmol) of 1, 0.52 g (2.9 mmol) of trans-stilbene, and
10 mg (0.01 mmol) of II were refluxed in 3 mL of CH2Cl2 for 48
h. The solvent was evaporated and the residue extracted three times
with cold hexanes. Column chromatography of the extract with a
5:1 hexanes/ethyl acetate eluent afforded 0.32 g (1.2 mmol, 81%
yield) of 5 as a white solid. For 5: mp ) 90-91 °C. NCI-HRMS
Physical Measurements. 1H NMR at 500.4 MHz, 13C NMR at
125.8 MHz, and 11B NMR spectra at 160.1 MHz were obtained on
a Bruker AMX 500 spectrometer. 11B NMR spectra at 128.4 MHz
were obtained on a Bruker DMX 400 spectrometer. All 11B NMR
chemical shifts are referenced to external BF3‚O(C2H5)2 (0.00 ppm)
12
11
(m/e): calcd for
C
B
1H20 262.2496, found 262.2500. Anal.
11 10
Calcd: C, 50.74; H, 7.74. Found: C, 50.46; H, 8.01. 11B NMR:
(160.1 MHz, CDCl3, ppm, J ) Hz): -4.1 (d, 1B, J 150), -7.5 (d,
1B, J 149), -10.9 (d, 2B, J 151), -12.9 (d, 2B, J 156), -14.8 (d,
1
1
with a negative sign indicating an upfield shift. All H chemical
4B, J 160). H NMR (500.4 MHz, CDCl3, ppm, J ) Hz): 7.32-
shifts were measured relative to residual protons in the lock solvents
and are referenced to Me4Si (0.00 ppm). High- and low-resolution
mass spectra (HRMS and LRMS) using negative chemical ioniza-
tion (NCI) techniques were recorded on a Micromass Autospec
spectrometer. Low-resolution mass spectra (LRMS) using electro-
spray ionization (ESI) techniques were recorded on an Agilent LC-
MS platform. Infrared spectra were recorded on a Perkin-Elmer
1430 IR spectrometer using NaCl plates or on a Perkin-Elmer 2000
FT-IR spectrometer using KBr pellets or NaCl plates. Elemental
analyses were performed at Robertson Microlit Laboratories,
Madison, NJ. Melting points were obtained on a standard melting
point apparatus and are uncorrected.
1,1′-(CH2CHdCHCH2)-(1,2-C2B10H11)2 (3). In a drybox, a two-
neck round-bottom flask equipped with a septum, stirbar, and
vacuum adapter was charged with 16.6 mg (0.02 mmol) of II. The
flask was sealed, taken out of the box, and slightly evacuated. Then,
0.5 mL of CH2Cl2 and 0.17 g (0.91 mmol) of 1 in 2 mL of CH2Cl2
were added through the septum. The reaction mixture was
submerged in a 45 °C oil bath and stirred for 48 h. Column
chromatography with hexanes and benzene eluents afforded 0.12
7.20 (m, 5H, C6H5), 6.37 (d, 1H, J 15.7, dCH), 5.98 (m, 1H, d
CH), 3.55 (s, br, 1H, cage C-H), 3.05 (d, 2H, J 7.7, dCHCH2).
IR (NaCl plate, cm-1): 3080 (m), 3040 (m), 2550 (vs), 1600 (w),
1490 (m), 1455 (s), 1075 (m), 965 (s), 765 (s), 730 (w), 695 (s).
1-[CH3C(O)OCH2CHdCHCH2]-1,2-C2B10H11 (6). As de-
scribed for 3, 0.17 g (0.92 mmol) of 1, 0.60 mL (3.8 mmol) of
cis-1,4-diacetoxy-2-butene, and 15 mg (0.02 mmol) of II were
refluxed in 2 mL of CH2Cl2 for 24 h. Column chromatography
with a 3:1 hexanes/ethyl acetate eluent afforded the crude product.
Vacuum distillation afforded 0.19 g (0.66 mmol, 84% yield) of 6
as a light colorless oil, which crystallized as a white solid at
0 °C. For 6: mp ) 23-24 °C. NCI-HRMS (m/e): calcd for
12C8
B
16O2 H20 258.2394, found 258.2402. Anal. Calcd: C,
11
1
10
37.48; H, 7.86. Found: C, 37.68; H, 7.81. 11B NMR (160.1 MHz,
CDCl3, ppm, J ) Hz): -4.3 (d, 1B, J 149), -7.6 (d, 1B, J 149),
-11.1 (d, 2B, J 150), -13.1 (d, 2B, J 167), -15.0 (d, 4B, J 158).
1H NMR (500.4 MHz, CDCl3, ppm, J ) Hz): 5.64 (m, 2H, d
CH), 4.56 (d, 2H, J 4.2, dCH-CH2), 3.60 (s, br, 1H, cage C-H),
2.97 (d, 2H, J 6.0, dCH-CH2), 2.08 (s, 3H, CH3). IR (NaCl plate,
cm-1): 3420 (br, m), 3030 (m), 2920 (m), 2560 (vs), 1710 (vs),
1430 (m), 1365 (s), 1345 (s), 1215 (vs), 1105 (m), 1040 (m), 1005
(s), 955 (s), 825 (w), 705 (s).
g (0.36 mmol, 79%) of 3 as a white solid. For 3: mp ) 278-280
°C. NCI-HRMS (m/e): calcd for 12C8
B
1H28 344.4052, found
11
20
344.4051. Anal. Calcd: C, 28.22; H, 8.29. Found: C, 28.45; H,
8.24. 11B NMR (160.1 MHz, CDCl3, ppm, J ) Hz): -3.8 (d, 2B,
J 148), -7.1 (d, 2B, J 142), -10.8 (d, 4B, J 150), -13.5 (d, 4B,
J 173), -14.7 (d, 8B, J 182). 1H NMR (500.4 MHz, C6D6, ppm, J
) Hz): 5.47 (t of t, 2H, J1 4.3, J2 1.8, dCH), 3.54 (s, br, 2H, cage
C-H), 2.97 (d, 4H, J 4.1, dCH-CH2). 13C NMR (125.8 MHz,
CDCl3): 129.5, 73.0, 60.3, 40.6. FT-IR (KBr pellet, cm-1): 3064
(s), 2924 (w), 2854 (w), 2590 (vs), 1618 (w), 1434 (m), 1355 (w),
1292 (w), 1212 (m), 1153 (m), 1123 (w), 1080 (w), 1051 (w), 1017
(m), 983 (m), 937 (w), 821 (w), 724 (m), 677 (w), 640 (w), 555
(w), 504 (w).
1-(C6H5CH2CHdCHCH2)-1,2-C2B10H11 (4). As described for
3, 0.38 g (1.8 mmol) of 1, 1.5 g (7.2 mmol) of 1,4-diphenyl-2-
butene,7 and 8 mg (0.01 mmol) of II were refluxed in 3 mL of
CH2Cl2 for 24 h. Column chromatography with hexanes eluted 1,4-
diphenyl-2-butene. Subsequent elution with benzene afforded 0.33
g (1.2 mmol, 62%) of 4 as a light yellow oil, which slowly
crystallized into a white solid at 0 °C. For 4: mp < room
1-(HOCH2CHdCHCH2)-1,2-C2B10H11 (7). As described for 3,
0.26 g (1.4 mmol) of 1, 0.72 mL (8.8 mmol) of 2-butene-1,4-diol,
and 19 mg (0.02 mmol) of II were refluxed in a cosolvent of 3 mL
of CH2Cl2 and 1.5 mL of THF for 16 h. Column chromotography
with benzene eluent afforded 0.23 g (1.1 mmol, 76% yield) of 7 as
a colorless oil. For 7: NCI-HRMS (m/e): calcd for 12C611B1016O11H18
216.2288, found 216.2294. 11B NMR (160.1 MHz, CDCl3, ppm, J
) Hz): -4.5 (d, 1B, J 148), -7.8 (d, 1B, J 148), -11.3 (d, 2B, J
150), -13.2 (d, 2B, J 166), -15.2 (d, 4B, J 157). 1H NMR (500.4
MHz, CDCl3, ppm, J ) Hz): 5.75 (m, 1H, dCH), 5.59 (m, 1H,
dCH), 4.16 (d, 2H, J 6.0, dCH-CH2), 3.61 (s, br, 1H, cage C-H),
2.89 (d, 2H, J 7.4, dCH-CH2), 1.81 (s, 1H, OH). IR (NaCl plate,
cm-1): 3580 (w), 3450 (s, br), 3020 (s), 2905 (m), 2840 (w), 2540
(vs), 1745 (m), 1685 (s), 1415 (s), 1355 (m), 1290 (w), 1210 (w),
1080 (s), 1045 (m), 980 (s), 955 (s), 870 (w), 775 (w), 705 (s).
1-(ClCH2CHdCHCH2)-1,2-C2B10H11 (8). As described for 3,
0.20 g (1.1 mmol) of 1, 1.2 mL (11.4 mmol) of cis-1,4-dichloro-
2-butene, and 21 mg (0.02 mmol) of II were refluxed in 2 mL of
CH2Cl2 for 15 h. Column chromatography with benzene eluent
afforded 0.26 g (0.92 mmol, 87% yield) of 8 as a light yellow oil.
(7) Blackwell, H. E.; O’Leary, D. J.; Chatterjee, A. K.; Washenfelder,
R. A.; Bussman, D. A.; Grubbs, R. H. J. Am. Chem. Soc. 2000, 122, 58-
71.
11
1
For 8: NCI-HRMS (m/e): calcd for 12C6 35Cl1 H17 234.1949,
B
10

Ru-Catalyzed Homo and Cross Metathesis Reactions
Organometallics, Vol. 25, No. 3, 2006 611
found 234.1955. Anal. Calcd: C, 30.96; H, 7.36. Found: C, 31.44;
H, 6.80. 11B NMR (160.1 MHz, CDCl3, ppm, J ) Hz): -4.3 (d,
1B, J 148), -7.6 (d, 1B, J 150), -11.1 (d, 2B, J 150), -13.3 (d,
2B, J ∼180), -15.0 (d, 4B, J 158). 1H NMR (500.4 MHz, CDCl3,
ppm, J ) Hz): 5.73 (m, 2H, dCH), 4.02 (d, 2H, J 5.9, dCH-
CH2), 3.57 (s, br, 1H, cage C-H), 2.98 (d, 2H, J 6.8, dCH-CH2).
IR (NaCl plate, cm-1): 3015 (s), 2920 (m), 2570 (vs), 2285 (w),
1415 (s), 1325 (w), 1265 (w), 1235 (s), 1190 (w), 1140 (w), 1100
(w), 1040 (m), 995 (m), 980 (w), 945 (s), 760 (w), 745 (w), 705
(s), 670 (w).
8.64. 11B NMR (160.1 MHz, CDCl3, ppm, J ) Hz): -4.5 (d, 1B,
J 150), -7.8 (d, 1B, J 147), -11.2 (d, 2B, J 151), -13.1 (d, 2B,
J 168), -15.0 (d, 4B, J 158). 1H NMR (500.4 MHz, CDCl3, ppm,
J ) Hz): 5.54 (m, 1H, dCH), 5.35 (m, 1H, dCH), 3.62 (s, br,
1H, cage C-H), 2.88 (d, 2H, J 7.5, dCH-CH2), 2.54 (t, 2H, J
7.0, dCHCH2CH2), 2.32 (m, 2H, dCH-CH2), 2.11 (s, 3H, CH3).
IR (NaCl plate, cm-1): 3030 (s), 2895 (m), 2550 (vs), 1685 (vs),
1410 (m), 1390 (m), 1340 (s), 1290 (w), 1205 (w), 1165 (w), 1140
(s), 1045 (m), 995 (s), 955 (s), 760 (w), 705 (s).
1-[t-C4H9OC(O)NHCH2CHdCHCH2]-1,2-C2B10H11 (13). As
described for 3, 0.15 g (0.82 mmol) of 1, 0.70 g (4.5 mmol) of
tert-butyl-N-allylcarbamate, and 27 mg (0.03 mmol) of II were
refluxed in 3 mL of CH2Cl2 for 48 h. Column chromatography
with benzene and 1:1 benzene/CH2Cl2 eluents followed by recrys-
tallization from hexanes afforded 0.18 g (0.57 mmol, 70% yield)
of 13 as a white solid. For 13: mp ) 108-110 °C. NCI-HRMS
1-(C6H5CH2OCH2CHdCHCH2)-1,2-C2B10H11 (9). As de-
scribed for 3, 0.17 g (0.92 mmol) of 1, 1.0 mL (3.9 mmol) of cis-
1,4-dibenzoxy-2-butene, and 15 mg (0.02 mmol) of II were refluxed
in 2 mL of CH2Cl2 for 15 h. Column chromatography with 3:1
and 1:1 hexanes/benzene eluents afforded 0.22 g (0.73 mmol, 79%
yield) of 9 as a colorless oil. For 9: NCI-HRMS (m/e): calcd for
12
11
1
11
1
C
B
16O1 H24 306.2758, found 306.2759. 11B NMR (160.1
(m/e): calcd for 12C11 14N116O2 H27 315.2972, found 315.2969.
B
10
13
10
MHz, CDCl3, ppm, J ) Hz): -1.3 (d, 1B, J 152), -4.7 (d, 1B, J
146), -8.3 (d, 2B, J 149), -10.2 (d, 2B, J 170), -12.0 (d, 4B, J
Anal. Calcd: C, 42.15; H, 8.68; N, 4.47. Found: C, 41.63; H, 8.35;
N, 4.29. 11B NMR (160.1 MHz, CDCl3, ppm, J ) Hz): -4.7 (d,
1B, J 147), -7.8 (d, 1B, J 147), -11.1 (d, 2B, J 150), -13.0 (d,
1
156). H NMR (500.4 MHz, CDCl3, ppm, J ) Hz): 7.40-7.33
1
(m, 5H, C6H5), 5.67 (m, 2H, dCH), 4.54 (s, 2H, CH2-C6H5), 4.02
(d, 2H, J 5.0, dCH-CH2), 3.56 (s, br, 1H, cage C-H), 2.97 (d,
2H, J 7.0, dCH-CH2). IR (NaCl plate, cm-1): 3125 (s), 3095 (s),
2980 (m), 2925 (s), 2680 (vs), 1490 (w), 1460 (m), 1440 (w), 1365
(m), 1205 (w), 1110 (m), 1085 (m), 980 (m), 795 (w), 745 (m),
720 (s), 680 (w).
2B, J 163), -15.1 (d, 4B, J 165). H NMR (500.4 MHz, CDCl3,
ppm, J ) Hz): 5.53 (m, 2H, dCH), 4.72 (s, br, 1H, NH), 3.81 (s,
br, 1H, cage C-H), 3.70 (t, 2H, J 5.2, dCH-CH2), 2.94 (d, 2H,
J 7.1, dCH-CH2), 1.46 (s, 9H, BOC-CH3). FT-IR (KBr pellet,
cm-1): 3345 (s), 3060 (m), 2982 (m), 2925 (w), 2582 (vs), 1753
(s), 1687 (vs), 1543 (s), 1536 (m), 1509 (m), 1441 (w), 1408 (m),
1390 (w), 1294 (m), 1259 (w), 1162 (s), 1053 (m), 1021 (w), 977
(s), 866 (w), 788 (w), 724 (w), 597 (w).
1-[CH3(CH2)3CHdCHCH2]-1,2-C2B10H11 (10). As described
for 3, 0.33 g (1.8 mmol) of 1, 3 mL of 1-hexene, and 10 mg (0.01
mmol) of II were refluxed in 3 mL of CH2Cl2 for 14 h. Column
chromatography with hexanes eluent afforded 0.38 g (1.6 mmol,
1-[NC(CH2)3CHdCHCH2]-1,2-C2B10H11 (14). As described for
3, 0.23 g (1.2 mmol) of 1, 2.0 g (21 mmol) of 5-cyano-1-pentene,
and 27 mg (0.03 mmol) of II were refluxed in 2 mL of CH2Cl2 for
14 h. Column chromatography with benzene and 1:1 benzene/CH2-
Cl2 eluents afforded 0.21 g (0.8 mmol, 66% yield) of 14 as a yellow
88% yield) of 10 as a colorless viscous oil. For 10: NCI-HRMS
11
(m/e): calcd for 12C9
B
1H24 242.2809, found 242.2809. Anal.
10
Calcd: C, 44.97; H, 10.06. Found: C, 44.60; H, 9.55. 11B NMR
(160.1 MHz, CDCl3, ppm, J ) Hz): -4.4 (d, 1B, J 148), -7.8 (d,
1B, J 148), -11.1 (d, 2B, J 151), -12.9 (d, 2B, J 165), -15.0 (d,
11
1
oil. For 14: NCI-HRMS (m/e): calcd for 12C9
B
14N1 H21
10
253.2605, found 253.2611. 11B NMR (160.1 MHz, CDCl3, ppm, J
) Hz): -4.4 (d, 1B, J 148), -7.8 (d, 1B, J 148), -11.3 (d, 2B, J
150), -13.3 (d, 2B, J 176), -15.1 (d, 4B, J 158). 1H NMR (500.4
MHz, CDCl3, ppm, J ) Hz): 5.48 (m, 2H, dCH), 3.58 (s, br, 1H,
cage C-H), 2.92 (d, 2H, J 7.0, dCH-CH2), 2.37 (t, 2H, J 7.0,
CH2CN), 2.27 (q, 2H, J 7.0, dCH-CH2), 1.78 (p, 2H, J 7.2, CH2).
IR (NaCl plate, cm-1): 3030 (s), 2905 (s), 2850 (m), 2815 (m),
2530 (vs), 2220 (m), 1710 (w), 1695 (w), 1650 (w), 1620 (w), 1430
(m), 1410 (s), 1340 (w), 1270 (w), 1245 (w), 1190 (w), 1100 (w),
995 (m), 950 (s), 770 (w), 705 (s).
1
4B, J 158). H NMR (500.4 MHz, CDCl3, ppm, J ) Hz): 5.55
(m, 1H, dCH), 5.30 (m, 1H, dCH), 3.55 (s, br, 1H, cage C-H),
2.89 (d, 2H, J 7.4, dCH-CH2), 2.06 (d, 2H, J 6.8, dCH-CH2),
1.34 (m, 4H, 2CH2), 0.91 (t, 3H, J 7.2, CH3). IR (NaCl plate, cm-1):
3080 (s), 2950 (s), 2915 (s), 2580 (vs), 1705 (w), 1660 (w), 1450
(m), 1430 (s), 1375 (w), 1290 (w), 1200 (w), 1110 (w), 1060 (m),
1010 (m), 960 (s), 930 (w), 715 (s).
1-[CF3C(O)OCH2CHdCHCH2]-1,2-C2B10H11 (11). As de-
scribed for 3, 0.24 g (1.3 mmol) of 1, 1.0 mL (7.7 mmol) of
allyltrifluoroacetate, and 28 mg (0.03 mmol) of II were refluxed
in 3 mL of CH2Cl2 for 5 h. Column chromatography with a 1:1
hexanes/benzene eluent afforded 0.31 g (1.2 mmol, 77% yield) of
11 as a colorless oil. For 11: NCI-HRMS (m/e): calcd for
1-{[(CH3)4C2O2]BCH2CHdCHCH2}-1,2-C2B10H11 (15). As
described for 3, 0.27 g (1.5 mmol) of 1, 1.0 mL (5.3 mmol) of
2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaboronate, and 20 mg (0.02
mmol) of II were refluxed in 3 mL of CH2Cl2 for 14 h. Column
chromatography with benzene eluent afforded 0.26 g (0.80 mmol,
55% yield) of 15 as a colorless oil, which slowly crystallized upon
standing. For 15: a white solid, mp ) 53-54 °C. NCI-HRMS (m/
11
1
12C8
B
19F316O2 H17 312.2111, found 312.2109. Anal. Calcd: C,
10
30.96; H, 5.52. Found: C, 31.41; H, 5.90. 11B NMR (160.1 MHz,
CDCl3, ppm, J ) Hz): -1.3 (d, 1B, J 151), -4.6 (d, 1B, J 150),
-8.3 (d, 2B, J 150), -10.5 (d, 2B, J 174), -11.7 (d, 4B, J 159).
1H NMR (500.4 MHz, CDCl3, ppm, J ) Hz): 5.80 (m, 1H, d
CH), 5.72 (m, 1H, dCH), 4.83 (d, 2H, J 6.0, dCH-CH2), 3.56 (s,
br, 1H, cage C-H), 3.01 (d, 2H, J 7.3, dCH-CH2). IR (NaCl
plate, cm-1): 3035 (m), 2915 (w), 2550 (vs), 1760 (vs), 1530 (w),
1435 (m), 1410 (w), 1375 (m), 1325 (s), 1205 (vs), 1150 (vs), 1045
(w), 995 (m), 950 (s), 930 (w), 905 (m), 845 (w), 815 (w), 755
(m), 705 (s).
12
11
1
e): calcd for
C
B
16O2 H29 326.3191, found 326.3181. Anal.
12 11
Calcd: C, 44.45; H, 9.01. Found: C, 44.24; H, 9.06. 11B NMR
(160.1 MHz, CDCl3, ppm, J ) Hz): 32.3 (s, 1B), -3.3 (d, 1B, J
119) -6.4 (d, 1B, J 147), -9.7 (d, 2B, J 146), -11.3 (d, 2B, J
172), -13.7 (d, 4B, J 156). 1H NMR (500.4 MHz, CDCl3, ppm, J
) Hz): 5.61 (m, 1H, dCH), 5.28 (m, 1H, dCH), 4.00 (s, br, 1H,
cage C-H), 2.88 (d, 2H, J 7.6, dCH-CH2), 1.70 (d, 2H, J 7.5,
dCH-CH2), 1.25 (s, 12H, -CH3). IR (NaCl plate, cm-1): 3000
(s), 2930 (s), 2550 (vs), 1640 (w), 1610 (w), 1445 (m), 1415 (m),
1360 (vs), 1245 (m), 1190 (m), 1140 (m), 1115 (vs), 1085 (m),
1055 (m), 995 (m), 945 (s), 855 (m), 820 (s), 765 (w), 700 (m),
650 (w).
1-[CH3C(O)(CH2)2CHdCHCH2]-1,2-C2B10H11 (12). As de-
scribed for 3, 0.23 g (1.2 mmol) of 1, 1.2 mL (10 mmol) of 5-hexen-
2-one, and 27 mg (0.03 mmol) of II were refluxed in 3 mL of
CH2Cl2 for 18 h. Column chromatography with 1:1 hexanes/benzene
and CH2Cl2 eluents afforded 0.22 g (0.87 mmol, 69% yield) of 12
as a light yellow oil, which slowly crystallized upon standing. For
2Cs+‚[7,7′-(CH2CHdCHCH2)-(7,8-C2B9H11)2]2- (16). Follow-
ing the procedure described by Do,8a 0.21 g (0.62 mmol) of 3 and
0.62 g of CsF (4.3 mmol) were dissolved in 20 mL of anhydrous
ethanol. After three cycles of freeze-pump-thaw, the mixture was
12: NCI-HRMS (m/e): calcd for 12C9
256.2591. Anal. Calcd: C, 42.50; H, 8.72. Found: C, 43.31; H,
B
10
16O1 H22 256.2601, found
11
1

612 Organometallics, Vol. 25, No. 3, 2006
Wei et al.
11
refluxed in vacuo until 11B NMR analysis showed complete
consumption of 3 (48 h). The solvent was vacuum evaporated and
the residue rinsed three times with cold deionized water and then
dried in vacuo. Recrystallization from ethanol afforded 0.25 g (0.36
for
C
B
1H44 384.5304, found 384.5316. Anal. Calcd: C,
10 20
12
31.55; H, 11.65. Found: C, 31.63; H, 11.86. 11B NMR (160.1 MHz,
CDCl3, ppm, J ) Hz): 24.2 (s, 2, B6), 8.5 (d, 4, B1,3, J 166), 6.8
(d, 2, B9, J 145), -0.8 (d, 4, B5,7, J 153), -4.6 (d, 4, B8,10, J
1
mmol, 58% yield) of 16 as a white solid. For 16: mp > 300 °C.
154), -35.7 (d, 2, B2, J 154), -40.5 (d, 2, B4, J 153). H NMR
11
ESI-LRMS: (m/e) calcd for 12C8
B
18
1H28 161, found 161. 11B NMR
(500.4 MHz, CDCl3, ppm, J ) Hz): 5.42 (t, 2H, J 5.1, dCH),
2.04 (d, 4H, J 5.5, dCH-CH2), 1.59 (m, 4H, CH2), 1.47 (m, 4H,
CH2), 1.38 (m, 4H, CH2), -1.71 (s, br, 4H, BHB), -2.02 (s, br,
4H, BHB). IR (NaCl plate, cm-1): 2940 (s), 2870 (m), 2590 (vs),
1920 (br, w), 1550 (w), 1535 (w), 1500 (s), 1440 (m), 1410 (m),
1095 (m), 1000 (s), 960 (m), 935 (w), 920 (w), 860 (w), 845 (m),
815 (m), 700 (br, m).
(160.1 MHz, CD3OD, ppm, J ) Hz): -11.0 (d, 4B, J 132), -13.6
(d, 2B, J 153), -17.2 (d, 2B, J 143), -18.5 (d, 4B, J 171), -21.9
1
(d, 2B, J 145), -33.5 (d, 2B, J 135), -37.2 (d, 2B, J 142). H
NMR (500.4 MHz, CD3OD, ppm, J ) Hz): 5.16 (m, 2H, dCH),
2.21 (m, 4H, dCH-CH2), 2.06 (s, br, 2H, cage C-H), -2.68 (s,
br, 2H, BHB). IR (NaCl plate, cm-1): 3370 (br, s), 2900 (s), 2480
(vs), 1640 (s), 1420 (w), 1180 (m), 1050 (m), 1010 (s), 970 (m).
Cs+[7-CH3(CH2)3CHdCHCH2-7,8-C2B9H11]- (17). As de-
scribed for 16, 0.30 g (1.2 mmol) of 10 was reacted with 0.38 g
(2.5 mmol) of CsF in 20 mL of anhydrous ethanol for 48 h under
reflux in vacuo.8a The ethanol was evaporated, and the residue was
rinsed three times with cold deionized water and dried in vacuo.
Recrystallization from cold ethanol/water afforded 0.40 g (1.1
mmol, 88% yield) of 17 as a white solid. For 17: mp > 300 °C.
6-[C6H5CH2CHdCH(CH2)4]-B10H13 (20). As described for 3,
0.38 g (1.8 mmol) of 2, 1.5 g (7.2 mmol) of 1,4-diphenyl-2-butene,7
and 8 mg (0.01 mmol) of II were refluxed in 2 mL of CH2Cl2, for
48 h. Column chromatography with 2% ethyl acetate in hexanes
separated the excess 1,4-diphenyl-2-butene, while elution with
benzene afforded 0.34 g (1.2 mmol, 62% yield) of 20 as a yellow
oil, which slowly crystallized into a light yellow solid upon standing.
For 20: mp ) 160-163 °C. NCI-HRMS (m/e): calcd for
1
ESI-LRMS (m/e): calcd for 12C911B9 H24 231, found 231. Anal.
1H29 (M-H) 295.3200, found 295.3206. Anal. Calc: C,
12
11
C
B
13
10
Calcd: C, 29.82; H, 6.67. Found: C, 29.80; H, 6.54. 11B NMR
(160.1 MHz, CD3OD, ppm, J ) Hz): -12.8 (d, 2B, J 130), -15.4
(d, 1B, J 153), -18.9 (d, 1B, J 146), -20.2 (d, 2B, J ∼134), -23.7
53.02; H, 10.27. Found: C, 52.60; H, 9.62. 11B NMR (160.1 MHz,
CDCl3, ppm, J ) Hz): 23.9 (s, 1, B6), 8.4 (d, 2, B1,3, J 147), 6.7
(d, 1, B9, J 165), -0.9 (d, 2, B5,7, J 153), -4.7 (d, 2, B8,10, J
1
1
(d, 1B, J 150), -35.2 (d, 1B, J ∼134), -38.9 (d, 1B, J 128). H
152), -35.9 (d, 1, B2, J 154), -40.6 (d, 1, B4, J 154). H NMR
NMR (500.4 MHz, CD3OD, ppm, J ) Hz): 5.44 (m, 1H, dCH),
5.24 (m, 1H, dCH), 2.04 (d, 2H, J 7.3, dCH-CH2), 1.95 (d, 2H,
J 6.6, dCH-CH2), 1.60 (s, 1H, cage C-H), 1.32 (m, 4H, 2CH2),
0.88 (t, 3H, J 7.0, CH3), -2.82 (s, br, 1H, BHB). FT-IR (KBr pellet,
cm-1): 3399 (br, s), 2592 (m), 2932 (m), 2860 (w), 2528 (vs),
2288 (w), 2044 (w), 1701 (w), 1654 (w), 1420 (vs), 1300 (s), 1072
(s), 925 (m), 782 (w), 721 (m).
(500.4 MHz, CDCl3, ppm, J ) Hz): 7.37-7.21 (m, 5H, C6H5),
5.62 (m, 1H, dCH), 5.54 (m, 1H, dCH), 3.37 (d, 2H, J 6.5, d
CH-CH2), 2.10 (q, 2H, J 7.0, dCH-CH2), 1.62 (m, 2H, CH2),
1.53 (m, 2H, CH2), 1.40 (m, 2H, CH2), -1.70 (s, br, 2H, BHB),
-2.01 (s, br, 2H, BHB). IR (NaCl plate, cm-1): 3220 (w), 3060
(w), 3020 (m), 2905 (s), 2575 (vs), 1955 (w), 1905 (w), 1605 (w),
1555 (m), 1495 (vs), 1450 (s), 1415 (vs), 1340 (s), 1095 (s), 1000
(s), 965 (s), 940 (w), 920 (w), 890 (w), 840 (w), 815 (m), 735 (s),
700 (s).
[N(C4H9)4]+[7-CH3(CH2)3CHdCHCH2-7,8-C2B9H11]- (18). Fol-
lowing the procedure reported by Wade,8b 0.20 g (0.83 mmol) of
10 dissolved in 5 mL of THF was added to 3.3 mL of a 1 M
tetrabutylammonium fluoride THF solution (3.3 mmol). The
reaction mixture was stirred at room temperature overnight.
Deionized water (10 mL) was added and the mixture then extracted
three times with 20 mL of CH2Cl2. The organic layer was separated,
filtered through silica gel, and then dried with MgSO4. The bulk
of the volatiles were removed via Rotovap, and the product was
further dried on the high-vacuum line to afford 0.33 g (0.70 mmol,
84% yield) of 18 as a waxy white solid. For 18: mp ) 96-97 °C.
6-[CH3C(O)OCH2CHdCH(CH2)4]-B10H13 (21). As described
for 3, 0.41 g (2.0 mmol) of 2, 1.5 mL (9.4 mmol) of cis-1,4-
diacetoxy-2-butene, and 8 mg (0.01 mmol) of II were refluxed in
3 mL of CH2Cl2 for 48 h. Column chromatography with a 4:1
hexanes/benzene eluent afforded 0.34 g (1.2 mmol, 61%) of 21 as
a light yellow solid. For 21: mp ) 162-164 °C. NCI-HRMS (m/
11
1
e): calcd for 12C9
B
16O2 H28 278.3020, found 278.3010. Anal.
10
Calcd: C, 39.11; H, 10.21. Found: C, 38.60; H, 9.98. 11B NMR
(160.1 MHz, CDCl3, ppm, J ) Hz): 24.0 (s, 1, B6), 8.1 (d, 2,
B1,3, J 146), 6.8 (d, 1, B9, J ∼129), -1.1 (d, 2, B5,7, J 165),
-4.8 (d, 2, B8,10, J 152), -35.8 (d, 1, B2, J 158), -40.6 (d, 1,
ESI-LRMS (m/e): calcd for 12C911B9 H24 231, found 231. 11B NMR
1
(160.1 MHz, CDCl3, ppm, J ) Hz): -13.1 (d, 2B, J 133), -16.0
(d, 1B, J 146), -20.1 (s, br, 3B), -24.3 (d, 1B, J 140), -35.7 (d,
1B, J ∼134), -39.4 (d, 1B, J 140). 1H NMR (500.4 MHz, CDCl3,
ppm, J ) Hz): 5.50 (m, 1H, dCH), 5.29 (m, 1H, dCH), 3.18 (t,
36H, J 8.6, CH3), 2.40 (d, 2H, J 6.0, dCH-CH2), 2.21 (d, 2H, J
7.1, dCH-CH2), 1.96 (m, 4H, 2CH2), 1.86 (s, 1H, cage C-H),
1.03 (t, 3H, J 7.3, CH3), -2.61 (s, br, 1H, BHB). FT-IR (KBr pellet,
cm-1): 3364 (s), 2963 (s), 2876 (s), 2521 (vs), 1420 (vs), 1304
(s), 1212 (w), 1134 (w), 1029 (m), 969 (w), 914 (m), 777 (m), 739
(m), 706 (w), 669 (w), 549 (w), 514 (w), 482 (w), 460 (w).
6,6′-[(CH2)4CHdCH(CH2)4]-(B10H13)2 (19). As described for
3, 0.25 g (1.2 mmol) of 2 and 8 mg (0.01 mmol) of I were stirred
in 2 mL of CH2Cl2 at room temperature for 24 h. Column
chromatography with hexanes and benzene eluents afforded 0.14
g (0.36 mmol, 61% yield) of 19 as a light yellow solid. Alterna-
tively, 0.40 g (2.0 mmol) of 2 and 8 mg of II (0.01 mmol) were
refluxed in 2 mL of CH2Cl2 for 36 h. Column chromatography
with hexanes and benzene eluents afforded 0.29 g (0.76 mmol, 78%
yield) of 19. For 19: mp ) 53-54 °C. NCI-HRMS (m/e) calcd
1
B4, J 154). H NMR (500.4 MHz, CDCl3, ppm, J ) Hz): 5.78
(m, 1H, dCH), 5.59 (m, 1H, dCH), 4.52 (d, 2H, J 6.4, dCH-
CH2), 2.14 (m, 2H, CH2), 2.10 (s, 3H, CH3), 1.58 (m, 2H, CH2),
1.49 (m, 2H, CH2), 1.38 (m, 2H, CH2), -1.71 (s, br, 2H, BHB),
-2.01 (s, br, 2H, BHB). IR (NaCl plate, cm-1): 2920 (s), 2865
(w), 2565 (vs), 1500 (m), 1475 (m), 1375 (m), 1285 (s), 1190 (w),
1020 (m), 1000 (m), 955 (m).
6-[C6H5CH2OCH2CHdCH(CH2)4]-B10H13 (22). As described
for 3, 0.27 g (1.3 mmol) of 2, 1.5 mL (5.8 mmol) of 1,4-cis-
dibenzoxy-2-butene, and 23 mg (0.02 mmol) of II were refluxed
in 3 mL of CH2Cl2 for 20 h. Column chromatography with a 1:1
benzene/hexanes eluent afforded 0.45 g (1.0 mmol, 76% yield) of
22 as a viscous yellow oil. For 22: NCI-HRMS (m/e): calcd for
16O1 H32 326.3384, found 326.3401. Anal. Calcd: C,
12
11
1
C
B
14
10
51.82; H, 9.94. Found: C, 52.44; H, 9.52. 11B NMR (160.1 MHz,
CDCl3, ppm, J ) Hz): 27.1 (s, 1, B6), 10.9 (d, 2, B1,3, J 149),
9.6 (d, 1, B9, J ∼126), 1.8 (d, 2, B5,7, J 161), -2.1 (d, 2, B8,10,
J 148), -32.7 (d, 1, B2, J 157), -37.5 (d, 1, B4, J 157). 1H NMR
(500.4 MHz, CDCl3, ppm, J ) Hz): 7.39-7.36 (m, 5H, C6H5),
5.73 (m, 1H, dCH), 5.63 (m, 1H, dCH), 4.53 (s, 2H, CH2-C6H5),
4.00 (d, 2H, J 6.2, dCH-CH2), 2.11 (q, 2H, J 7.0, dCH-CH2),
1.61 (m, 2H, CH2), 1.52 (t, 2H, J 6.2, CH2), 1.40 (m, 2H, CH2),
(8) (a) Yoo, J.; Hwang, J.; Do, Y. Inorg. Chem. 2001, 40, 568-570. (b)
Fox, M. A.; Gill, W. R.; Herbertson, P. L.; MacBride, J. A. H.; Wade K.;
Colquhoun, H. M. Polyhedron 1996, 15, 565-571. (c) Wiesboeck, R. A.;
Hawthorne, M. F. J. Am. Chem. Soc. 1964, 86, 1642.

Ru-Catalyzed Homo and Cross Metathesis Reactions
Organometallics, Vol. 25, No. 3, 2006 613
11
-1.71 (s, br, 2H, BHB), -2.01 (s, br, 2H, BHB). IR (NaCl plate,
cm-1): 3085 (w), 3205 (m), 3005 (s), 2895 (vs), 2810 (vs), 2550
(vs), 1940 (w), 1880 (w), 1785 (w), 1655 (w), 1530 (m), 1480 (s),
1420 (s), 1395 (m), 1340 (m), 1295 (w), 1245 (w), 1185 (w), 1075
(s), 1040 (m), 985 (s), 950 (s), 915 (m), 820 (w), 795 (w), 725
(m), 715 (m), 680 (m), 655 (m).
mp < room temperature. NCI-HRMS (m/e): calcd for 12C12
B
10
1H28
282.3122, found 282.3111. Anal. Calcd: C, 51.39; H, 10.06.
Found: C, 50.60; H, 11.01. 11B NMR (160.1 MHz, CDCl3, ppm,
J ) Hz): 23.8 (s, 1, B6), 8.5 (d, 2, B1,3, J 147), 6.8 (d, 1, B9, J
142), -0.8 (d, 2, B5,7, J 151), -4.6 (d, 2, B8,10, J 152), -35.8
1
(s, 1, B2, J 154), -40.5 (d, 1, B4, J 154). H NMR (500.4 MHz,
CDCl3, ppm, J ) Hz): 7.38-7.20 (m, 5H, C6H5), 6.41 (d, 1H, J
15.9, dCH), 6.23 (m, 1H, dCH), 2.27 (m, 2H, dCH-CH2), 2.04
(m, 2H, CH2), 1.58 (m, 2H, CH2), 1.42 (m, 2H, CH2), -1.71 (s,
br, 2H, BHB), -2.03 (s, br, 2H, BHB). IR (NaCl plate, cm-1):
3015 (m), 2920 (s), 2860 (m), 2595 (vs), 1930 (w), 1725 (w), 1650
(w), 1605 (w), 1550 (m), 1500 (s), 1450 (m), 1435 (m), 1415 (m),
1315 (m), 1100 (s), 1005 (s), 965 (s), 920 (w), 865 (w), 845 (w),
815 (m), 720 (w), 700 (m).
6-[ClCH2CHdCH(CH2)4]-B10H13 (23). As described for 3, 0.40
g (2.0 mmol) of 2, 2.0 mL (24.5 mmol) of allyl chloride, and 8 mg
(0.01 mmol) of II were refluxed in 2 mL of CH2Cl2 for 14 h.
Column chromatography with a 1:1 benzene/hexanes eluent af-
forded 0.33 g (1.3 mmol, 67% yield) of 23 as a viscous light yellow
11
1
oil. For 23: NCI-HRMS (m/e): calcd for 12C7
B
35Cl1 H25
10
254.2575, found 254.2552. Anal. Calcd: C, 33.25; H, 9.97.
Found: C, 33.24; H, 9.76. 11B NMR (160.1 MHz, CDCl3, ppm, J
) Hz): 23.8 (s, 1, B6), 8.5 (d, 2, B1,3, J 147), 6.8 (d, 1, B9, J
164), -0.9 (d, 2, B5,7, J 154), -4.6 (d, 2, B8,10, J 152), -35.8
6-[CH3C(O)(CH2)2CHdCH(CH2)4]-B10H13 (27). As described
for 3, 0.19 g (1.0 mmol) of 2, 1.0 mL (8.6 mmol) of 5-hexen-2-
one, and 16 mg (0.02 mmol) of II were refluxed in 3 mL of CH2-
Cl2 for 20 h. Column chromatography with benzene eluent afforded
0.15 g (0.6 mmol, 57% yield) of 27 as a yellow oil. For 27: NCI-
1
(d, 1, B2, J 154), -40.5 (d, 1, B4, J 154). H NMR (500.4 MHz,
CDCl3, ppm, J ) Hz): 5.79 (m, 1H, dCH), 5.65 (m, 1H, dCH),
4.05 (d, 2H, J 7.1, dCH-CH2), 2.12 (q, 2H, J 7.1, dCH-CH2),
1.57 (m, 2H, CH2), 1.51 (m, 2H, CH2), 1.38 (m, 2H, CH2), -1.72
(s, br, 2H, BHB), -2.03 (s, br, 2H, BHB). IR (NaCl plate, cm-1):
2895 (s), 2815 (m), 2515 (vs), 1880 (w), 1695 (s), 1645 (w), 1545
(m), 1515 (m), 1475 (s), 1415 (s), 1350 (w), 1225 (s), 1075 (m),
1020 (w), 980 (s), 940 (s), 910 (w), 895 (w), 840 (w), 815 (w),
790 (m), 705 (m), 665 (m).
12
11
1
HRMS (m/e): calcd for
C
B
16O1 H30 276.3227, found
10 10
276.3221. 11B NMR (160.1 MHz, CDCl3, ppm, J ) Hz): 27.1 (s,
1, B6), 11.1 (d, 2, B1,3, J 148), 9.5 (d, 1, B9, J ∼152), 2.0 (d, 2,
B5,7, J 155), -2.0 (d, 2, B8,10, J 154), -32.8 (d, 1, B2, J 150),
1
-37.6 (d, 1, B4, J 160). H NMR (500.4 MHz, CDCl3, ppm, J )
Hz): 5.41 (m, 2H, dCH), 2.49 (t, 2H, J 8.2, dCH-CH2), 2.30
(m, 2H, dCH-CH2), 2.16 (s, 3H, CH3), 2.03 (m, 2H, CH2), 1.53
(m, 2H, CH2), 1.43 (m, 2H, CH2), 1.36 (m 2H, CH2), -1.68 (s, br,
2H, BHB), -1.97 (s, br, 2H, BHB). IR (NaCl plate, cm-1): 2915
(vs), 2875 (s), 2570 (vs), 1910 (w), 1695 (vs), 1555 (m), 1505 (s),
1440 (s), 1410 (s), 1355 (s), 1260 (w), 1240 (w), 1160 (m), 1095
(m), 1005 (s), 965 (s), 935 (w), 920 (w), 865 (w), 840 (w), 820
(w), 725 (m), 710 (w), 690 (w).
6-[CH3(CH2)3CHdCH(CH2)4]-B10H13 (24). As described for 3,
0.26 g (1.3 mmol) of 2, 2.0 mL of 1-hexene, and 10 mg (0.01
mmol) of II were refluxed in 3 mL of CH2Cl2 overnight. Column
chromatography with hexanes eluent afforded the crude product,
which was then vacuum distilled (85 °C, 7 mmHg) to afford 0.33
g (1.3 mmol, 78% yield) of 24 as a colorless oil. For 24: NCI-
10
HRMS (m/e): calcd for 12C10
B
1H32 262.3434, found 262.3440.
10
11B NMR (160.1 MHz, CDCl3, ppm, J ) Hz): 24.0 (s, 1, B6), 8.4
(d, 2, B1,3, J 147), 6.7 (d, 1, B9, J 164), -0.9 (d, 2, B5,7, J 157),
-4.7 (d, 2, B8,10, J 153), -35.8 (d, 1, B2, J 154), -40.6 (d, 1,
6-[CH3CH2OCH2CHdCH(CH2)4]-B10H13 (28). As described
for 3, 0.21 g (1.1 mmol) of 2, 2.0 mL (17.6 mmol) of allylethyl
ether, and 17 mg (0.02 mmol) of II were heated at 30 °C in 1 mL
of CH2Cl2 for 30 h. Column chromatography with a 1:1 benzene/
CH2Cl2 eluent afforded 0.19 g (0.73 mmol, 70% yield) of 28 as a
1
B4, J 153). H NMR (500.4 MHz, CDCl3, ppm, J ) Hz): 5.41
(m, 2H, dCH), 2.02 (m, 4H, 2CH2), 1.56 (m, 2H, CH2), 1.42 (m,
4H, 2CH2), 1.37 (m, 2H, CH2), 1.32 (m, 2H, CH2), 0.96 (t, 3H, J
5.7, CH3), -1.72 (s, br, 2H, BHB), -2.02 (s, br, 2H, BHB). IR
(NaCl plate, cm-1): 2915 (s), 2900 (vs), 2815 (s), 2540 (vs), 2305
(w), 1900 (w), 1795 (m), 1580 (w), 1485 (m), 1445 (m), 1425 (m),
1360 (w), 1345 (w), 1080 (m), 990 (s), 950 (s), 795 (m), 705 (m).
11
1
yellow oil. For 28: NCI-HRMS (m/e): calcd for 12C9
B
10
16O1 H29
(M-H) 263.3149, found 263.3157. 11B NMR (160.1 MHz, CDCl3,
ppm, J ) Hz): 24.0 (s, 1, B6), 8.4 (d, 2, B1,3, J 146), 6.7 (d, 1,
B9, J 161), -0.9 (d, 2, B5,7, J 156), -4.7 (d, 2, B8,10, J 148),
-35.8 (d, 1, B2, J 154), -40.6 (d, 1, B4, J 153). 1H NMR (500.4
MHz, CDCl3, ppm, J ) Hz): 5.62 (m, 1H, dCH), 5.51 (m, 1H,
dCH), 3.85 (d, 2H, J 6.1, dCH-CH2), 3.42 (m, 2H, dCH-CH2),
2.03 (q, 2H, J 7.0, CH2), 1.50 (m, 2H, CH2), 1.40 (m, 2H, CH2),
1.31 (m, 2H, CH2), 1.15 (t, 3H, J 6.9, CH3), -1.80 (s, br, 2H,
BHB), -2.10 (s, br, 2H, BHB). IR (NaCl plate, cm-1): 2950 (m),
2905 (s), 2815 (s), 2540 (vs), 1900 (br, w), 1655 (w), 1540 (w),
1485 (m), 1425 (m), 1355 (w), 1335 (w), 1245 (w), 1075 (vs), 980
(s), 945 (m), 915 (w), 895 (w), 865 (w), 840 (w), 820 (w), 795
(w), 705 (m), 690 (w), 670 (w).
6-[CF3C(O)OCH2CHdCH(CH2)4]-B10H13 (25). As described
for 3, 0.33 g (1.6 mmol) of 2, 1.2 mL (9.2 mmol) of allyltri-
fluoroacetate, and 31 mg (0.03 mmol) of II were refluxed in 3 mL
of CH2Cl2 for 18 h. Column chromatography with a 4:1 benzene/
hexanes eluent afforded 0.42 g (1.3 mmol, 79% yield) of 25 as a
colorless oil. For 25: NCI-HRMS (m/e): calcd for 12C9
B
10
37O2
-
11
19
1
F3 H25 332.2737, found 332.2727. Anal. Calcd: C, 32.72; H, 7.63.
Found: C, 33.01; H, 7.66. 11B NMR (160.1 MHz, CDCl3, ppm, J
) Hz): 27.3 (s, 1, B6), 11.1 (d, 2, B1,3, J 149), 9.9 (d, 1, B9, J
148), 1.9 (d, 2, B5,7, J 156), -1.8 (d, 2, B8,10, J 151), -32.7 (d,
6-[CH3OC(O)CHdCH(CH2)4]-B10H13 (29). As described for
3, 0.32 g (1.6 mmol) of 2, 0.6 mL of inhibitor-free methylacrylate,
and 10 mg (0.01 mmol) of II were refluxed in 3 mL of CH2Cl2 for
48 h. Column chromatography with a 1:1 hexanes/benzene eluent
followed by drying in vacuo at 60 °C gave 0.38 g (1.4 mmol, 91%
yield) of 29 as a white solid. For 29: mp ) 98-100 °C. NCI-
HRMS (m/e): calcd for 12C810B1016O21H26 264.2863, found 264.2855.
Anal. Calcd: C, 36.62; H, 9.99. Found: C, 36.47; H, 9.77. 11B
NMR (160.1 MHz, CDCl3, ppm, J ) Hz): 23.8 (s, 1, B6), 8.4 (d,
2, B1,3, J 148), 7.0 (d, 1, B9, J 156), -0.9 (d, 2, B5,7, J 156),
-4.6 (d, 2, B8,10, J 148), -35.8 (d, 1, B2, J 154), -40.4 (d, 1,
B4, J 153). 1H NMR (500.4 MHz, CDCl3, ppm, J ) Hz): 6.88 (d
of t, 1H, J1 15.6, J2 6.9, dCH), 5.75 (d, 1H, J 15.6, dCH), 3.65 (s,
3H, CH3), 2.17 (m, 2H, dCH-CH2), 1.49 (m, 4H, 2CH2), 1.34
(m, 2H, CH2), -1.74 (s, br, 2H, BHB), -2.07 (s, br, 2H, BHB).
IR (NaCl plate, cm-1): 3020 (w), 2930 (s), 2885 (m), 2540 (vs),
1
1, B2, J 158), -37.5 (d, 1, B4, J 157). H NMR (500.4 MHz,
CDCl3, ppm, J ) Hz): 5.92 (m, 1H, dCH), 5.63 (m, 1H, dCH),
4.80 (d, 2H, J 6.7, dCH-CH2), 2.16 (m, 2H, dCH-CH2), 1.57
(m, 2H, CH2), 1.52 (m, 2H, CH2), 1.38 (m, 2H, CH2), -1.73 (s,
br, 2H, BHB), -2.01 (s, br, 2H, BHB). IR (NaCl plate, cm-1):
2905 (vs), 2860 (s), 2560 (vs), 1950 (br, w), 1775 (s), 1665 (w),
1550 (w), 1495 (m), 1445 (w), 1395 (w), 1340 (m), 1215 (m), 1145
(s), 1090 (m), 995 (m), 965 (m), 910 (w), 855 (w), 835 (w), 810
(w), 775 (w), 725 (m).
6-[C6H5CHdCH(CH2)4]-B10H13 (26). As described for 3, 0.23
g (1.1 mmol) of 2, 0.6 mL of inhibitor-free styrene, and 8 mg (0.01
mmol) of II were stirred in 2 mL of CH2Cl2 at 30 °C for 60 h.
Column chromatography with a 5:1 hexanes/ethyl acetate eluent
afforded 0.29 g (1.0 mmol, 92% yield) of 26 as a yellow oil, which
was then recrystallized from cold CH2Cl2. For 26: a white solid,

614 Organometallics, Vol. 25, No. 3, 2006
Wei et al.
1940 (w), 1700 (vs), 1660 (m), 1560 (w), 1505 (m), 1435 (s), 1315
(m), 1285 (s), 1205 (s), 1185 (m), 1160 (w), 1100 (m), 1040 (w),
1005 (s), 975 (m), 920 (w), 910 (w), 855 (w), 845 (w), 815 (w),
740 (m).
1-[1-(1,2-C2B10H11)]-CH2CHdCH(CH2)4-7-(6-B10H13) (30). As
described for 3, 0.72 g (3.9 mmol) of 1, 0.20 g (1.0 mmol) of 2,
and 36 mg (0.04 mmol) of II were refluxed in 5 mL of CH2Cl2 for
18 h. Column chromatography with benzene eluent, followed by
solvent evaporation afforded the crude product, which was then
extracted with hexanes and further purified on silica gel using a
4:1 hexanes/benzene eluent. Recrystallization from toluene afforded
Figure 1. Structures of the Grubbs “first-generation” Cl2Ru(d
CHPh)(PCy3)2 (I) and “second-generation” Cl2Ru(dCHPh)(PCy3)(H2-
IMes) (II) catalysts.
0.28 g (0.8 mmol, 71% yield) of 30 as a white solid. For 30: mp
10
) 68-69 °C. NCI-HRMS (m/e): calcd for 12C9
B
1H35 (M-H)
20
363.4600, found 363.4600. 11B NMR (128.4 MHz, CDCl3, ppm, J
) Hz): 24.2 (s, 1B), 8.7 (d, 2B, J 145), 7.1 (d, 1B, J 163), -0.6
(d, 2B, J 147), -4.3 (d, 3B, J 146), -7.6 (d, 1B, J 146), -11.0 (d,
2B, J 152), -12.9 (d, 2B, J 180), -14.6 (d, 4B, J 155), -35.6 (d,
5, the two independent molecules of the asymmetric unit adopt
different conformations with the phenyl rings in different orienta-
tions. The double bonds also adopted two different orientations in
each of the independent molecules, which according to least-squares
refinement had relative populations of 0.778:0.222 for molecule 1
and 0.510:0.490 for molecule 2. In 15, one of the two independent
molecules in the asymmetric unit had the CdC bond disordered in
two orientations with relative populations of 0.70 and 0.30. In the
second molecule, the pinacolborane group was disordered by a
rotation of approximately 75° about the C-B bond with relative
populations of 0.60 and 0.40.
1
1B, J 153), -40.2 (d, 1B, J 154). H NMR (500.4 MHz, CDCl3,
ppm, J ) Hz): 5.55 (m, 1H, dCH), 5.34 (m, 1H, dCH), 3.56 (s,
br, 1H, cage-CH), 2.91 (d, 2H, J 7.4, dCH-CH2), 2.11 (m, 2H,
dCH-CH2), 1.57 (m, 2H, CH2), 1.48 (m, 2H, CH2), 1.37 (m, 2H,
CH2), -1.72 (s, br, 2H, BHB), -2.01 (s, br, 2H, BHB). FT-IR
(KBr pellet, cm-1): 3217 (w), 3068 (m), 2925 (s), 2854 (m), 2575
(vs), 1902 (br, w), 1701 (w), 1633 (w), 1559 (w), 1501 (s), 1429
(m), 1265 (m), 1203 (w), 1098 (br, w), 1042 (w), 1017 (m), 1006
(s), 973 (m), 932 (w), 919 (w), 882 (w), 860 (w), 837 (w), 811
(m), 722 (m), 704 (w), 685 (w), 669 (w), 642 (w), 605 (w).
Crystallographic Data for Compounds 3, 5, 13, 15, and 30.
Single crystals were grown from a 1:1 acetone/heptane solution of
3 (Upenn # 3213) at room temperature, from a CH2Cl2 solution of
5 (Upenn # 3224) at -20°C, from a hexanes solution of 13 (Upenn
# 3248) at room temperature, from a hexanes solution of 15 (Upenn
# 3247) at -20 °C, and from a toluene solution of 30 (Upenn #
3253) at room temperature.
Results and Discussion
Because of their high reactivity, stability, and functional group
tolerance,3,14 the Grubbs ruthenium complexes, Cl2Ru(dCHPh)-
(PCy3)L, L ) PCy3 (I) and H2IMes (II) (Figure 1), were
employed as catalysts for the metathesis reactions of the two
alkenylpolyboranes 1-(CH2dCHCH2)-1,2-C2B10H11 (1) and
6-[CH2dCH(CH2)4]-B10H13 (2).
Collection and Reduction of the Data. X-ray intensity data were
collected on a Rigaku Mercury CCD area detector employing
graphite-monochromated Mo KR (λ ) 0.71069 Å) radiation at a
temperature of 143 K. Indexing was performed from a series of
four 0.5° oscillation images with exposure of 30 s per frame for 3
and a series of twelve 0.5° rotation images with exposures of 30 s
for 5, 13, 15, and 30 with a crystal-to-detector distance of 36 mm
for all crystals. Oscillation images were processed using Crystal-
Clear,9 producing a listing of unaveraged F2 and σ(F2) values, which
were then passed to the CrystalStructure10 program package for
further processing and structure solution on a Dell Pentium III
computer. The intensity data were corrected for Lorentz and
polarization effects. Absorption corrections were made for 3, 13,
15, and 30 using REQAB.11
Homometathesis of 1-(CH2dCHCH2)-1,2-C2B10H11 (1). In
a typical reaction (eq 1), 1 was heated in CH2Cl2 solution under
gentle reflux in vacuo in the presence of II. Evolution of
ethylene gas was immediately observed, and a white precipitate
of 3 formed toward the end of the reaction. The reaction was
determined to be complete (48 h when using 2 mol % of II)
when the terminal olefinic resonances of 1 disappeared in the
1H NMR spectrum.
Solution and Refinement of the Structures. The structures were
solved by direct methods (SIR97).12 Refinements were by full-
matrix least squares based on F2 using SHELXL-97.13 All reflec-
tions were used during refinement (F2’s that were experimentally
negative were replaced by F2 ) 0). Non-hydrogen atoms were
refined anisotropically, cage hydrogen atoms were refined isotro-
pically, and chain hydrogen atoms were included as constant
contributions to the structure factors and were not refined. Disorder
was found in the structures of 3, 5, and 15 and were refined
accordingly. For 3, disorder was observed with the C14-C14*
double bond assuming two different orientations in a 4:1 ratio. For
3 was separated from the catalyst residue via column
chromatography using step elution with hexanes and benzene.
Recrystallization from acetone/heptane cosolvent gave air-stable
white crystals in 79% yield. 3 is soluble in polar solvents
including CH2Cl2, CHCl3, THF, and acetone, while being
partially soluble in benzene and toluene and completely
insoluble in hexanes.
(9) CrystalClear; Rigaku Corporation, 1999.
(10) CrystalStructure, Crystal Structure Analysis Package; Rigaku
Corporation, 2002.
(11) REQAB: Jacobsen, R. A. Private communication, 1994.
(12) SIR97: Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, G.;
Giacovazzo, C.; Moliterni, A.; Polidori, G.; Spagna, R. J. Appl. Crystallogr.
1999, 32, 115-119.
(13) Sheldrick, G. M. SHELXL-97, Program for the Refinement of Crystal
Structures; University of Go¨ttingen: Germany, 1997.
The 11B NMR spectrum of 3 was nearly identical to that of
1, showing the five-line doublet pattern in 1:1:2:2:4 ratios

Ru-Catalyzed Homo and Cross Metathesis Reactions
Organometallics, Vol. 25, No. 3, 2006 615
a crystallographic inversion center passing through the midpoint
of the double bond. The C14-C14* (1.321(4) Å) bond length
and the C13-C14-C14* (123.3(3)°) bond angle confirm the
C14-C14* double bond and the sp2 hybridization of C14.
The olefin-linked o-carborane compounds 1,1′-(CHdCH)-
2,2′-R,R′-(1,2-C2B10H10)2 (R, R′ ) Ph, n-Bu, p-MeC6H4; R )
Ph, R′ ) p-MeC6H4) have previously been synthesized in yields
of 45-80% via the reactions of ene-diynes with decaborane.17
The homometathesis route used for the synthesis of 3 provides
a more convenient high-yield route to these types of high boron
content materials.
1 showed different reactivities with the I and II catalysts.
With 5 mol % of I, only ∼10% conversion of 1 was observed
by 1H NMR after 24 h, but nearly complete reaction was
observed when 1 was refluxed with 5 mol % of II in CH2Cl2
for the same reaction period.
Grubbs has classified olefins into four different categories
based on both their ability to undergo homometathesis and the
ability of their homodimers to undergo secondary metathesis
in the presence of metathesis catalysts.18 Electron-rich and
sterically unhindered olefins are type-I olefins. They undergo
self-metathesis readily, and their homodimers are active for cross
metatheses. Examples of type-I olefins for the II catalyst include
terminal olefins such as 1-alkenes, allylbenzene, allylsilane, allyl
esters, and allyl ethers. Electron-deficient olefins, including
acrylates and sterically hindered olefins such as vinyl boronates
and vinyl dioxolanes, are type-II olefins. They undergo ho-
mometathesis reactions at reduced rates, but participate in cross
metathesis reactions with more active type-I olefins. Type-III
olefins do not self-metathesize, but can still participate in cross
metathesis. Type-IV olefins, including highly electron-deficient
and sterically bulky olefins, do not undergo metathesis.
On the basis of its homometathesis and cross metathesis (vide
infra) reactivities, 1, like styrene, would be classified as a type-I
olefin for II and a type-II olefin for I.18 The reduced reactivity
with I is probably a result of the influence of the bulky
o-carborane weakening the metal-olefin bonding interaction.
Consistent with this observation, it was found that 1-(CH2d
CH)-1,2-C2B10H11, which has an even larger steric hindrance
because of the carborane being directly attached to the vinyl
group, did not homometathesize with either of the I or II
catalysts.
Cross Metathesis Reactions of 1-(CH2dCHCH2)-1,2-
C2B10H11 (1). The synthetic utility of cross metathesis reactions
can be limited by the unwanted homometathesis reactions of
the individual olefinic partners. However, the reaction of a type-I
olefin and a different type-I olefin homodimer has been shown
to preferably form the cross metathesis product when an excess
of the homodimer is used to suppress the homodimerization of
the free olefin partner.7,18 Accordingly, where they were
available, type-I olefin dimers were favored as cross metathesis
partners in our studies in order to enhance the selectivity for
cross metathesis. That is, the II-catalyzed cross metathesis of
the type-I olefin 1 with an excess of a type-I olefin homodimer
should produce the cross metathesis product with high selectivity
since the formation of 3 (the homodimer of 1) would be greatly
suppressed. Indeed, reaction of 1 with an excess of 1,4-diphenyl-
2-butene (the homodimer of the type-I olefin allylbenzene)
catalyzed by II afforded 1-(C6H5CH2CHdCHCH2)-1,2-C2B10H11
Figure 2. ORTEP representation of the structure of 1,1′-(CH2-
CHdCHCH2)-(1,2-C2B10H11)2 (3). Selected bond distances (Å) and
angles (deg): C1-C2, 1.648(2); C1-B3, 1.724(2); C1-B4, 1.705-
(2); C1-B5, 1.706(2); C1-B6, 1.727(2); C1-C13, 1.528(2); C13-
C14, 1.496(2); C14-C14*, 1.321(4); C13-C1-C2, 120.14(9);
C13-C1-B3, 118.00(10); C13-C1-B4, 120.68(9); C13-C1-
B5, 119.93(10); C13-C1-B6, 116.67(9); C1-C13-C14, 114.65-
(11); C13-C14-C14*, 123.3(3).
characteristic of mono-C-substituted o-carborane derivatives.15
1
In its H NMR spectrum, the terminal olefinic resonances at
5.17 and 5.65 ppm in the spectrum of 1 were replaced by a
single olefinic intensity-two triplet centered at 5.34 ppm. This
resonance was coupled to the intensity-four doublet methylene
resonance at 2.98 ppm. The broad intensity-one carborane C-H
peak was found at 3.38 ppm. The 13C NMR spectrum of 3
showed a single intensity-two peak at 129.5 ppm, rather than
the two peaks (120.5 and 132.8 ppm) found6a in the spectrum
of 1. The close proximity of the bulky o-carborane cage to the
double bond would be expected to favor a trans-product,16 and,
as determined by 1H NMR integration, the trans- and cis-isomers
of 3 were produced in a 17:1 ratio. The IR spectrum of 3
showed, like the spectra of 4-30, a strong B-H absorption
near 2590 cm-1 and the CdC stretch near 1618 cm-1
.
An X-ray crystallographic determination of trans-3 confirmed
a structure composed of two mono-C-substituted o-carborane
cages linked by a -CH2CHdCHCH2- chain (Figure 2), with
(14) For some examples of the applications and advantages of ruthenium-
catalyzed cross metathesis reactions, see: (a) Chatterjee, A. K.; Grubbs,
R. H. Org. Lett. 1999, 1, 1751-1753. (b) Chatterjee, A. K.; Morgan, J. P.;
Scholl, M.; Grubbs, R. H. J. Am. Chem. Soc. 2000, 122, 3783-3784. (c)
Choi, T.-L.; Chatterjee, A. K.; Grubbs, R. H. Angew. Chem., Int. Ed. 2004,
40, 1277-1279. (d) Chatterjee, A. K.; Choi, T.-L.; Grubbs, R. H. Synlett
2001, 1034-1037. (e) Choi, T.-L.; Lee, C. W.; Chatterjee, A. K.; Grubbs,
R. H. J. Am. Chem. Soc. 2001, 123, 10417-10418. (f) Goldberg, S. D.;
Grubbs, R. H. Angew. Chem., Int. Ed. 2002, 41, 807-810. (g) Chatterjee,
A. K.; Sanders, D. P.; Grubbs, R. H. Org. Lett. 2002, 4, 1939-1942. (h)
Toste, F. D.; Chatterjee, A. K.; Grubbs, R. H. Pure Appl. Chem. 2002, 74,
7-10. (i) Chatterjee, A. K.; Toste, F. D.; Choi, T.-L.; Grubbs, R. H. AdV.
Synth. Catal. 2002, 344, 634-637. (j) Chatterjee, A. K.; Grubbs, R. H.
Angew. Chem., Int. Ed. 2002, 41, 3171-3174.
(15) Todd, L. J.; Siedle, A. R. Prog. NMR Spectrosc. 1993, 13, 87-
176.
(16) (a) Ulman, M.; Grubbs, R. H. Organometallics 1998, 17, 2484-
2489. (b) Sanford, M. S.; Ulman, M.; Grubbs, R. H. J. Am. Chem. Soc.
2001, 123, 749-750.
(17) (a) Yu, U. L.; Sladkov, A. M.; Gorshkov, V. I. Z. Org. Khim. 1968,
4, 25-27. (b) Thomas, R. L.; Rosair, G. M.; Welch, A. J. Chem. Commun.
1996, 11, 1327-1328.
(18) Chatterjee, A. K.; Choi, T.-L.; Sanders, D. P.; Grubbs, R. H. J.
Am. Chem. Soc. 2003, 125, 11360-11370.

616 Organometallics, Vol. 25, No. 3, 2006
Table 1. Crystallography Data Collection and Structural Refinement Information
Wei et al.
3
5
13
15
30
C9B20H36
360.58
empirical formula
fw
C8B20H28
340.50
C11B10H20
260.37
C11B10H27NO2
313.44
C12B11H29O2
324.26
cryst class
space group
Z
monoclinic
P21/c (#14)
2
triclinic
P1h (#2)
4
orthorhombic
P212121 (#19)
4
triclinic
P1h (#2)
4
orthorhombic
Pna21 (#33)
4
a, Å
b, Å
c, Å
6.6668(7)
13.4716(13)
11.5792(11)
11.0159(11)
12.366(2)
12.610(2)
113.458(2)
94.507(2)
100.690(2)
1526.2(3)
0.54
8.5581(5)
10.3974(8)
20.577(2)
11.3607(10)
12.2813(11)
14.8379(13)
95.676(2)
99.914(2)
100.532(2)
1986.7(3)
0.59
16.981(2)
19.783(2)
6.9346(6)
R, deg
â, deg
91.366(9)
γ, deg
V, Å3
1039.7(2)
0.46
1831.0(2)
0.64
2340.2(4)
0.44
µ, cm-1
cryst size, mm
0.35 × 0.27 × 0.10
0.38 × 0.27 × 0.15
0.32 × 0.30 × 0.18
0.22 × 0.20 × 0.06
0.42 × 0.18 × 0.08
D
calc, g/cm3
1.088
1.133
1.137
1.084
1.023
F(000)
352
544
664
688
760
radiation
2θ angle, deg
temp, K
Mo KR
6.04-50.66
143
Mo KR
5.28-50.68
233
Mo KR
5.16-50.68
143
Mo KR
5.08-50.68
143
Mo KR
5.22-50.08
143
hkl collected
-6 e h e 8,
-14 e k e 15,
-11 e l e 13
5970
-11 e h e 13,
-13 e k e 14,
-14 e l e 14
12 440
-10 e h e 10,
-12 e k e 11,
-23 e l e 24
15 693
-13 e h e 12,
-13 e k e 14,
-17 e l e 15
17 501
-20 e h e 20,
-23 e k e 18,
-8 e l e 7
10 257
no. of reflns measd
no. of unique reflns
1801 (Rint
0.0171)
1632
)
5353 (Rint
0.0589)
4501
)
3136 (Rint
0.0293)
3013
)
7171 (Rint
0.02111)
5546
)
3472 (Rint
0.0419)
2263
)
no. of obsd reflns (F > 4σ)
no. of reflns used in refinement
no. of params
1801
180
5353
520
3136
326
7171
524
3472
263
Ra indices (F > 4σ)
R1 ) 0.0464
wR2 ) 0.1242
R1 ) 0.0505
wR2 ) 0.1286
1.061
R1 ) 0.0525
wR2 ) 0.1312
R1 ) 0.0638
wR2 ) 0.1401
1.059
R1 ) 0.0464
wR2 ) 0.1476
R1 ) 0.0500
wR2 ) 0.1602
1.167
R1 ) 0.0835
wR2 ) 0.2200
R1 ) 0.1033
wR2 ) 0.2397
1.099
R1 ) 0.0766
wR1 ) 0.1956
R1 ) 0.0945
wR2 ) 0.2179
0.985
Ra indices (all data)
GOFb
final diff peaks, e/Å3
+0.196, -0.242
+0.239, -0.245
+0.372, -0.400
+1.010, -0.842
+0.332, -0.207
2
2
2
2
2
a R1 ) ||Fo| - |Fc||/|Fo|; wR2 ) {w(Fo - Fc )2/w(Fo )2}1/2
.
b GOF ) {w(Fo - Fc )2/n - p)}1/2 where n ) no. of reflections; p ) no. of parameters
refined.
(4) in ∼60% yield (Table 2, entry 1) with the excess 1,4-
diphenyl-2-butene then easily recovered after the reaction by
column chromatography. As shown in Scheme 1 and Table 2
(entries 2-6), the same protocol (1 + excess type-I olefin dimer)
was used for the II-catalyzed cross metathesis reactions of 1
with the olefin homodimers trans-stilbene, cis-1,4-diacetoxy-
2-butene, 2-butene-1,4-diol, 1,4-dichloro-2-butene, and cis-1,4-
dibenzoxyl-2-butene to give the cross metathesis products
1-(C6H5CHdCHCH2)-1,2-C2B10H11 (5), 1-[CH3C(O)OCH2-
CHdCHCH2]-1,2-C2B10H11 (6), 1-(HOCH2CHdCHCH2)-1,2-
C2B10H11 (7), 1-(ClCH2CHdCHCH2)-1,2-C2B10H11 (8), and
1-(C6H5CH2OCH2CHdCHCH2)-1,2-C2B10H11 (9), in yields of
76-87%.
In cases where a homodimer was not readily available, the
cross metathesis reactions of 1 with another type-I olefin partner
were employed. For reactions involving two individual type-I
olefinic partners, it has also been previously shown that a large
excess of one olefin partner can be used to suppress the
homometathesis of the other partner and favor the cross
metathesis product.7,18 Thus, the II-catalyzed reaction of the
type-I olefin 1 with a large excess of another type-I olefin should
favor cross metathesis, and, indeed, the II-catalyzed cross
metathesis reaction of 1 with a large excess of 1-hexene afforded
1-[CH3(CH2)3CHdCHCH2]-1,2-C2B10H11 (10) (Table 2, entry
7) in excellent yield (88%). The other product of the reaction,
5-decene (the homodimer of 1-hexene), was easily separated
from 10 via column chromatography. A similar method (1 +
excess type-I olefin) was used for the II-catalyzed reactions of
1 with the terminal olefins (Table 2, entries 8-12) allyltrifluo-
roacetate, 5-hexen-2-one, tert-butyl-N-allylcarbamate, 5-cyano-
1-pentene, and 2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaboronate
to give 1-[CF3C(O)OCH2CHdCHCH2]-1,2-C2B10H11 (11),
1-[CH3C(O)(CH2)2CHdCHCH2]-1,2-C2B10H11 (12), 1-[t-C4H9-
OC(O)NHCH2CHdCHCH2]-1,2-C2B10H11 (13), 1-[NC(CH2)3-
CHdCHCH2]-1,2-C2B10H11 (14), and 1-{[(CH3)4C2O2]BCH2-
CHdCHCH2}-1,2-C2B10H11 (15) in 55-88% yields.
I was found to have poor activity for the cross metathesis
reactions of 1. For example, when 1 was treated with the type-I
dimer 1,4-diphenyl-2-butene, in the presence of 5 mol % of I,
only low conversion of 1 occurred (<20% as determined by
1H NMR). Thus, all the cross metathesis reactions employed II
as the catalyst and were performed by heating a mixture of 1,
excess metathesis partner, and II in CH2Cl2 solution under gentle
reflux in vacuo. The reactions were monitored using TLC and
1H NMR. They were considered complete when the limiting
reagent 1 was completely consumed. The products were then
separated from the catalyst residue via step elution using column
chromatography on silica gel and further purified by recrystal-
lization or vacuum distillation.
Compounds 4-14 are air and water stable. The pinacolborane
group of 15 slowly hydrolyzes in air so it must be stored under
an inert atmosphere. All compounds showed good solubility in
polar solvents including THF, methylene chloride, chloroform,
and ethyl acetate. The less polar products 4, 5, and 14 were
also soluble in hexanes, benzene, and toluene.
The 11B NMR spectra of 4-15 are nearly identical to that of
1
3, showing five doublets in 1:1:2:2:4 ratios. Their H NMR
spectra showed resonances characteristic of their internal olefinic
protons and organic fragments, as well as broad B-H reso-
nances between 1 and 3 ppm, and a broad intensity-one
o-carborane C-H singlet. Integration of the olefinic proton
resonances arising from the cis- and trans-conformations of the
double bond again showed that the trans-products were favored.

Ru-Catalyzed Homo and Cross Metathesis Reactions
Organometallics, Vol. 25, No. 3, 2006 617
Table 2. Cross Metathesis Reactions of 1 with Functional
Olefins Catalyzed by II
Figure 3. ORTEP representation of the structure of 1-(C6H5CHd
CHCH2)-1,2-C2B10H11 (5). Selected bond distances (Å) and angles
(deg): C1-C2, 1.645(2); C1-B3, 1.729(2); C1-B4, 1.703(2); C1-
B5, 1.710(2); C1-B6, 1.733(2); C1-C13, 1.529(2); C13-C14,
1.494(3); C14-C15, 1.323(3); C15-C16, 1.488(2); C13-C1-C2,
119.69(12); C13-C1-B3, 119.26(13); C13-C1-B4, 122.07(13);
C13-C1-B5, 119.55(12); C13-C1-B6, 115.62(14); C1-C13-
C14, 116.7(2); C13-C14-C15, 124.9(2); C14-C15-C16, 126.7-
(2); C15-C16-C17, 120.81(14); C15-C16-C21, 119.14(14).
a See Experimental Section for reactant ratios and workup procedures.
1
b Determined by integration of H NMR.
Scheme 1. Cross Metathesis Reactions of
1-(CH2dCHCH2)-1,2-C2B10H11 (1) with Functional Olefins
Catalyzed by II
Figure 4. ORTEP representation of the structure of 1-[t-C4H9OC-
(O)NHCH2CHdCHCH2]-1,2-C2B10H11 (13). Selected bond dis-
tances (Å) and angles (deg): C1-C2, 1.658(3); C1-B3, 1.722(3);
C1-B4, 1.713(3); C1-B5, 1.712(3); C1-B6, 1.726(3); C1-C13,
1.514(3); C13-C14, 1.501(3); C14-C15, 1.322(3); C15-C16,
1.504(3); C16-N17, 1.448(3); N17-C18, 1.341(3); C18-O19,
1.347(2); C18-O20, 1.223(3); O19-C21, 1.482(2); C21-C22,
1.522(3); C21-C23, 1.518(3); C21-C24, 1.517(3); C13-C1-C2,
118.8(2); C13-C1-B3, 116.7(2); C13-C1-B4, 121.2(2); C13-
C1-B5, 121.7(2); C13-C1-B6, 117.4(2); C1-C13-C14, 113.6-
(2); C13-C14-C15, 122.3(2); C14-C15-C16, 126.1(2); C15-
C16-N17, 115.0(2); C16-N17-C18, 121.6(2); O19-C18-O20,
125.2(2); C18-O19-C21, 119.7(2); O19-C21-C22, 102.4(2);
O19-C21-C23, 111.5(2); O19-C21-C24, 108.6(2).
As summarized in Table 1 and Figures 3-5, the structures
of the trans-isomers of 1-(C6H5CHdCHCH2)-1,2-C2B10H11 (5)
(Figure 3), 1-[t-C4H9OC(O)NHCH2CHdCHCH2]-1,2-C2B10H11
(13) (Figure 4), and 1-{[(CH3)4C2O2]BCH2CHdCHCH2}-1,2-

618 Organometallics, Vol. 25, No. 3, 2006
Wei et al.
C2B10H11 (15) (Figure 5) were confirmed by single-crystal X-ray
determinations. The C14-C15 bond lengths (1.323(3) Å (5),
1.322(3) Å (13), and 1.324(4) Å (15)) and the ∼120° bond
angles of C13-C14-C15 and C14-C15-C16 in each structure
confirm a C14-C15 double bond. In 13, the C16-N17-C18-
O19 unit adopts the trans-conformation about the N17-C18
bond, which has been found in similar structures. The N17-
C18 (1.341(3) Å) and C18-O19 (1.347(2) Å) bonds are
significantly shorter than the respective C16-N17 (1.448(3) Å)
and O19-C21 (1.482(2) Å) single bonds, suggesting, as was
observed in the structure of BOC-glycine (t-C4H9OC(O)NHCH2-
COOH),19 that the C18-O20 double bond imposes some
double-bond character on the adjacent N17-C18 and C18-
O19 bonds.
In the reactions with allylbenzene and BOC-NHCH2CHd
CH2, olefin isomerization occurred to convert some of the
starting olefins into their Ph-CHdCHMe and BOC-NHCHd
CHCH3 isomers. Likewise, the isomerization of 1 to form
1-(CH3CHdCH)-1,2-C2B10H11 was observed in these reactions
(eq 2). It has been previously reported that ruthenium carbene
complexes rearrange in CH2Cl2 solution to generate binuclear
species responsible for olefin isomerizations.20
Figure 5. ORTEP representation of 1-{[(CH3)4C2O2]BCH2CHd
CHCH2}-1,2-C2B10H11 (15). Selected bond distances (Å) and angles
(deg): C1-C2, 1.650(4); C1-B3, 1.716(4); C1-B4, 1.701(4); C1-
B5, 1.707(4); C1-B6, 1.725(4); C1-C13, 1.533(3); C13-C14,
1.482(3); C14-C15, 1.324(4); C15-C16, 1.487(4); C16-B17,
1.572(4); B17-O18, 1.360(3); B17-O21, 1.370(3); O18-C19,
1.464(3); C19-C20, 1.566(4); C20-O21, 1.461(3); C19-C22,
1.520(4); C19-C23, 1.514(4); C20-C24, 1.522(4); C20-C25,
1.516(4); C13-C1-C2, 118.9(2); C13-C1-B3, 117.2(2); C13-
C1-B4, 121.2(2); C13-C1-B5, 121.0(2); C13-C1-B6, 116.9-
(2); C1-C13-C14, 115.3(2); C13-C14-C15, 124.7(3); C14-
C15-C16, 127.1(4); C15-C16-B17, 118.2(2); C16-B17-O18,
124.2(2); C16-B17-O21, 122.2(2); O18-B17-O21, 113.5(2);
B17-O18-C19, 107.8(2); O18-C19-C20, 102.0(2); C19-C20-
O21, 102.6(2); C22-C19-C23, 110.0(2); C24-C20-C25, 110.8-
(2).
Deboronation of 3 and 10: Formation of Dicarbollide Salts
16, 17, and 18. Employing the method reported by Do,8a when
3 was reacted with a large excess of CsF in dry ethanol under
reflux in vacuo for 48 h, deboronation of each of the o-carborane
cages occurred to afford 2Cs+‚[7,7′-(CH2CHdCHCH2)-7,8-
(C2B9H11)2]2- (16) in moderate yield (eq 3). Following recrys-
tallization from ethanol and water, 16 was obtained as a white
solid that was soluble in hot water and mixtures of water and
ethanol.
resonances, 16 showed only seven doublets in ratios of 2:1:1:
2:1:1:1 in its 11B NMR spectrum. The two high-field peaks at
-33.5 and -37.2 ppm are characteristic of the dicarbollide B10
and B1 borons, while the doublet at -33.5 ppm has fine splitting
characteristic of bridge-hydrogen coupling leading to its as-
signment to the B10 boron.15 The 16 1H NMR spectrum showed,
in addition to the resonances arising from the -CH2CHd
CHCH2- chain and the cage C-H, a broad upfield singlet at
-2.68 ppm that can be assigned to the bridging hydrogen
attached at the B9 and B10 edge.
Compound 10, 1-[CH3(CH2)3CHdCHCH2]-1,2-C2B10H11,
was likewise converted to the dicarbollide salts Cs+ (17) and
+
-
N(C4H9)4 (18) 7-[CH3(CH2)3CHdCHCH2]-7,8-C2B9H11 in
good yields (88% for 17 and 75% for 18) by treatment with
CsF in refluxing ethanol and tetrabutylammonium fluoride
(TBAF) in THF at room temperature, respectively (eq 4).8
The two cages in 16 are symmetry related, with each cage
having C1 symmetry, but owing to accidental overlap of several
(19) (a) Wade, L. G., Jr. Organic Chemistry, 5th ed.; Prentice Hall: New
Jersey, 2003. (b) Semertzidis, M.; Matsoukas, J.; Nastopoulos, V.; Voliotis,
S.; Leban, I. Acta Crystallogr. 1989, C45, 1474-1475.
(20) (a) Ulman, M.; Grubbs, R. H. J. Org. Chem. 1999, 64, 7202-7207.
(b) Hong, S. H.; Day, M. W.; Grubbs, R. H. J. Am. Chem. Soc. 2004, 126,
7414-7415.

Ru-Catalyzed Homo and Cross Metathesis Reactions
Organometallics, Vol. 25, No. 3, 2006 619
Scheme 2. Cross Metathesis Reactions of
6-[CH2dCH(CH2)4]-B10H13 (2) with Functional Olefins
Catalyzed by II
The cesium salt 17 was soluble in alcohol and in water at
elevated temperatures. The TBA salt 18 was not soluble in
water, but was very soluble in organic solvents including CH2-
Cl2, THF, and methanol.
The 11B NMR spectra of 17 and 18 were similar to that of
1
16. Their H NMR spectra showed, in addition to the peaks
assigned to the alkenyl chains and the tetrabutylammonium
group of 18, the cage C-H singlet and a broad upfield singlet
(at -2.82 ppm for 17 and at -2.61 ppm for 18) for the bridging
hydrogen.
Homometathesis of 6-[CH2dCH(CH2)4]-B10H13 (2). As
shown in eq 5, when 6-[CH2dCH(CH2)4]-B10H13 (2) was
reacted with I and II, the homodimer 6,6′-[(CH2)4CHdCH-
(CH2)4]-(B10H13)2 (19) was obtained in 61% and 78% yields,
respectively. Thus, according to the Grubbs classification, 2 is
a type-I olefin for both the I and II catalysts. The terminal
double bond in 2 is not in close proximity to the bulky
decaborane cage, and catalyst access for both the I and II
catalysts is thus apparently not sterically hindered.
Table 3. Cross Metathesis Reactions of 2 with Functional
Olefins Catalyzed by II
The metathesis reactions were performed in CH2Cl2 in vacuo
at room temperature for I and under gentle reflux for II.
Ethylene gas was formed within 5 min, and the reaction was
determined to be complete when the 1H NMR spectrum showed
complete consumption of 2. The waxy, light yellow solid of 19
was then purified from the metal residue by column chroma-
tography with stepwise elution of hexanes and benzene followed
by precipitation from hexanes at -78 °C.
Compound 19 is stable under an inert atmosphere, but slowly
hydrolyzes in air over days. It is soluble in benzene, toluene,
methylene chloride, and chloroform, but is soluble in hexanes
only at elevated temperatures.
The two decaborane clusters in 19 are symmetry related, so
its 11B NMR spectrum showed the downfield singlet and five
doublets in a 1:2:1:2:2:2 ratio that are characteristic of 6-R-
B10H13 derivatives.15 The 1H NMR spectrum showed the vinyl
and methylene resonances of the olefinic intercage bridge, the
overlapped terminal B-H resonances, and two broad, intensity-
four resonances (at -1.71 and -2.01 ppm) arising from the
decaborane bridging hydrogens.
Compounds with two decaborane clusters linked by saturated
linear and cyclic hydrocarbon bridges have been previously
synthesized by the metal-catalyzed hydroboration of dienes,6b,c
but 19 is the first example of a compound bearing two
decaborane clusters linked by an unsaturated carbon chain.
Cross Metathesis Reactions of 6-[CH2dCH(CH2)4]-B10H13
(2). Although 2 is a type-I olefin for both the I and II catalysts,
II was used in the cross metathesis reactions of 2 to take
advantage of its higher catalytic activity. The reactions (Scheme
2) were performed and worked up in the manner described for
the cross metathesis reactions of 1, again using an excess of
the olefinic homodimer (where available) or excess olefin
a See Experimental Section for reactant ratios and workup procedures.
1
b Determined by integration of H NMR.
partner to favor the formation of the cross metathesis product.
As can be seen in Table 3, when 2 was treated with an excess
of the olefinic homodimers 1,4-dipenyl-2-butene, cis-1,4-
diacetoxy-2-butene, and cis-1,4-dibenzoxyl-2-butene in the
presence of II, 6-[C6H5CH2CHdCH(CH2)4]-B10H13 (20),
6-[CH3C(O)OCH2CHdCH(CH2)4]-B10H13 (21), and 6-[C6H5-
CH2OCH2CHdCH(CH2)4]-B10H13 (22) were formed in 61-
76% yields, respectively, while reaction of 2 with an excess of
the terminal olefins allyl chloride, 1-hexene, allyltrifluoroacetate,

620 Organometallics, Vol. 25, No. 3, 2006
Wei et al.
Scheme 3. Different Approaches for the Preparation of
spectra showed the resonances of the olefinic bridge, the
substituents attached by cross metathesis, and two broad upfield
peaks assigned to the two sets of intensity-two decaborane
bridging hydrogens. In cases where the olefinic peaks for the
trans- and cis-isomers were resolved, integration again showed
that the trans-conformation was favored.
6-[C6H5CHdCH(CH2)4]-B10H13 (26)
Cross Metathesis of 1-(CH2dCHCH2)-1,2-C2B10H11 (1)
with 6-[CH2dCH(CH2)4]-B10H13 (2). The cross metathesis
reaction of 1 and 2 afforded 1-[1-(1,2-C2B10H11)]-CH2CHdCH-
(CH2)4-7-(6-B10H13) (30), with the o-carborane and decaborane
clusters linked via an olefinic bridge (eq 6).
styrene, 5-hexen-2-one, allylethyl ether, and methylacrylate gave
6-[ClCH2CHdCH(CH2)4]-B10H13 (23), 6-[CH3(CH2)3CHdCH-
(CH2)4]-B10H13 (24), 6-[CF3C(O)OCH2CHdCH(CH2)4]-B10H13
(25), 6-[C6H5CHdCH(CH2)4]-B10H13 (26), 6-[CH3C(O)(CH2)2-
CHdCH(CH2)4]-B10H13 (27), 6-[CH3CH2OCH2CHdCH(CH2)4]-
B10H13 (28), and 6-[CH3OC(O)CHdCH(CH2)4]-B10H13 (29) in
57-92% yields, respectively.
As shown in Scheme 3, three different methods can be
employed to synthesize 26: (1) reaction of 2 with excess styrene
catalyzed by II, which afforded 26 along with trans- and cis-
stilbene (the styrene homodimer); (2) reaction of 2 with excess
trans-stilbene catalyzed by II; and (3) reaction of 2 with excess
styrene catalyzed by I. In principle, method (3) should be the
most selective since, according to the Grubbs model, styrene
behaves as a type-II olefin for I and homometathesizes slowly.
Using this method, 26 was, in fact, obtained selectively with
no formation of either trans- or cis-stilbene; however, the
reaction was too slow to be synthetically useful. Method (1)
proved to be best since it employed an inexpensive starting
material, provided high reactivity and selectivity, and allowed
easy product separation by recrystallization.
Some olefins that were active for the cross metathesis
reactions of 1 failed to react with 2. 5-Cyano-1-pentene was
completely unreactive, while 2-butene-1,4-diol degraded the
decaborane cage by direct reaction. For the reactions of 2 with
the BOC-protected allylamine BOC-NHCH2CHdCH2 and al-
lylpinacolborane, olefin isomerization rather than cross metath-
esis was favored. Olefin isomerization to form benzylpropene
CH3CHdCHC6H5 also occurred in the reactions of 2 with
allylbenzene and lowered the yield of the cross metathesis
product 20. Thus, since it avoids olefin isomerization, the
reaction of 2 and 1,4-diphenyl-2-butene catalyzed by II is the
most useful method for the synthesis of 20.
The I-catalyzed cross metathesis of the type-II olefin 1 with
the type-I olefin 2 should in principle afford 30 selectively, but
the reaction was too slow to be practical. Both 1 and 2 are type-I
olefins with II, and the II-catalyzed reaction of 1 and 2 in a
1:4 ratio produced both 30 and 19 (the homodimer of 2), but it
was not possible to separate these products by either column
chromatography or recrystallization. The most convenient
methods for the synthesis of 30 were by either the II-catalyzed
reaction of an excess of 1 with 2 or the reaction of excess 3
(the homodimer of 1) with 2. Both of these methods gave
product mixtures containing 30 and 3 that could then be readily
separated by recrystallization from cold hexanes.
The 11B NMR spectrum of 30 showed patterns characteristic
of both clusters, i.e., the five-doublets for the o-carborane cluster
and the one singlet and six doublets for the decaborane cluster,
in a 1:1 ratio. The 30 1H NMR spectrum showed the resonances
of the olefinic bridge, overlapping broad terminal B-H
resonances in the 1-3 ppm region, the o-carborane CH
resonance at 3.56 ppm, and two broad upfield singlets at -1.72
and -2.01 ppm assigned to the two sets of decaborane bridging
hydrogens. According to the integration of the olefinic reso-
nances in the 1H NMR spectrum, the trans double-bond
conformation was favored (5.5 trans/cis ratio).
As shown in Figure 6, a single-crystal X-ray crystallographic
study confirmed that 30 has a structure composed of decaborane
and o-carborane clusters linked by a seven-carbon chain with
the C13-C14-C15 (121.1(4)°) and C14-C15-C16 (125.6-
(5)°) bond angles and C14-C15 (1.333(6) Å) bond length
confirming a double bond between C14 and 15.
Compounds 20-29 were stable under an inert atmosphere,
but slowly hydrolyzed upon standing in air over days. All
compounds were soluble in polar solvents, including methylene
chloride, chloroform, and ethyl acetate. Compounds 20, 22, 24,
26, and 28 were also soluble in the less polar solvents hexanes,
toluene, and benzene.
Conclusions
The results described above have clearly demonstrated that
alkenylpolyborane ruthenium-catalyzed olefin metathesis reac-
tions provide access to a variety of important polyborane
compounds. Both 1-(CH2dCHCH2)-1,2-C2B10H11 (1) and
6-[CH2dCH(CH2)4]-B10H13 (2) underwent homometathesis, as
well as cross metathesis reactions with each other, to produce
The 11B NMR spectra of 20-29 again showed patterns
1
characteristic of 6-substituted decaboranes.15 Their H NMR

Ru-Catalyzed Homo and Cross Metathesis Reactions
Organometallics, Vol. 25, No. 3, 2006 621
for medical (boron neutron capture therapy)21 applications. As
will be presented in a subsequent paper, the 3 and 19 carborane
and decaborane homodimers can also be employed in ruthenium-
catalyzed cross metatheses reactions with other olefin partners
to provide high-yield access to an even wider array of func-
tionalized polyboranes, including amino acid derivatives.
The ruthenium-catalyzed cross metathesis reactions of 1
provide mild, high-yield routes to alkenyl o-carborane deriva-
tives containing phenyl (4, 5), acetate (6, 11), alcohol (7), halide
(8), ether (9), alkenyl (10), ketone (12), protected-amine (13),
cyanide (14), and pinacolborane (15) functionalities. Metal-
catalyzed Suzuki-coupling reactions22 involving the pinacolbo-
rane group of 15 should make this derivative especially useful
for the syntheses of an even wider array of functional carboranes.
Likewise, as illustrated by the syntheses of 16, 17, and 18, a
range of new water-soluble, functionalized dicarbollide salts that
may also have applications for boron neutron capture therapy21
should now be possible via deboronation reactions.
The corresponding ruthenium-catalyzed cross metathesis
reactions of 2 have also provided the first routes to functional
decaborane derivatives, including phenyl (20, 26), acetate (21),
ether (22, 28), chloride (23), alkenyl (24), trifluoroacetate (25),
ketone (27), and enoic ester (29) functionalized compounds. The
high yields and selectivies of these reactions suggest that
ruthenium-catalyzed cross metathesis reactions may prove useful
for the functionalization of even more reactive polyboranes. We
are presently exploring these possibilities.
Figure 6. ORTEP representation of the structure of 1-[1-(1,2-
C2B10H11)]-CH2CHdCH(CH2)4-7-(6-B10H13) (30). Selected bond
distances (Å) and angles (deg): C1-C2, 1.640(5); C1-B3, 1.741-
(7); C1-B4, 1.712(5); C1-B5, 1.703(6); C1-B6, 1.701(6); C1-
C13, 1.529(5); C13-C14, 1.464(6); C14-C15, 1.333(6); C15-
C16, 1.473(6); C16-C17, 1.535(6); C17-C18, 1.519(6); C18-
C19, 1.527(6); C19-B6′, 1.571(6); B2′-B6′, 1.742(6); B5′-B6′,
1.795(7); B6′-B7′, 1.813(6); B8′-B9′, 1.770(7); B4′-B9′, 1.726-
(7); B9′-B10′, 1.787(8); C13-C1-C2, 120.8(3); C13-C1-B3,
117.5(4); C13-C1-B4, 119.5(3); C13-C1-B5, 119.4(3); C13-
C1-B6, 117.7(4); C1-C13-C14, 115.6(4); C13-C14-C15,
121.1(4); C14-C15-C16, 125.6(5); C15-C16-C17, 112.4(4);
C16-C17-C18, 110.3(4); C17-C18-C19, 113.8(4); C18-C19-
B6′, 114.4(4).
Acknowledgment. We thank the National Science Founda-
tion and the U.S. Department of Energy, Office of Basic Energy
Sciences, for the support of this project.
Supporting Information Available: CIF files for 3, 5, 13, 15,
and 30. This material is available free of charge via the Internet at
http://pubs.acs.org.
OM050851L
(21) (a) Hawthorne, M. F. Angew. Chem., Int. Ed. Engl. 1993, 32, 950-
984. (b) Soloway, A. H.; Tjarks, W.; Barnum, B. A.; Rong, F.-G.; Barth,
R. F.; Codogni, I. M.; Wilson, J. G. Chem. ReV. 1998, 98, 1515-1562. (c)
Hawthorne, M. F.; Maderna, A. Chem. ReV. 1999, 99, 3421-3434. (d)
Valliant, J. F.; Guenther, K. J.; King, A. S.; Morel, P.; Schaffer, P.; Sogbein,
O. O.; Stephenson, K. A. Coord. Chem. ReV. 2002, 232, 173-230.
(22) For a general review, see: Suzuki, A. Organoboranes in Organic
Syntheses; Hokkaido University: Sapparo, Japan, 2004; Chapter 5, pp 157-
226.
olefin-bridged compounds 3, 19, and 30 containing two po-
lyborane clusters. The high boron content of these compounds
suggests potential applications both as single-source precursors
to boron-based ceramic materials and as high-boron platforms