5502 Organometallics, Vol. 17, No. 25, 1998
Parks et al.
Ta ble 5. Su m m a r y of Da ta Collection a n d
Str u ctu r e Refin em en t Deta ils for 1
4-bromo-1-butene (7.3 µL, 0.072 mmol) and borane 1 (25.0 mg,
0.072 mmol). 1H NMR: δ 2.90 (t, J ) 6.3 Hz, 2H, CH2Br), 1.68
(br t, J ) 7.6 Hz, 2H, BCH2), 1.45-1.60 (m, 4H, CH2CH2). 13
C
formula
fw
space group
cryst syst
a, Å
C24H2B2F20
691.88
C2/c
monoclinic
43.925(7)
6.527(1)
18.770(3)
111.215(2)
5016.4(5)
Z
8
NMR: δ 147.1, 143.7, 137.7, and 114.0 (C6F5), 35.3 (CH2Br),
32.6 (CH2), 30.9 (BCH2), 23.4 (CH2). 19F NMR: δ -130.5 (d, J
) 20.0 Hz, Fo), -146.9 (t, J ) 20.7 Hz, Fp), -160.8 (m, Fm).
11B NMR: δ 72.7 (360).
F(000)
2688
1.832
0.211
8724
3212
0.0584
0.1219
1.081
d
calc, mg m-3
µ, mm-1
no. of reflcns
ind. reflcns
R1
b, Å
c, Å
Bis(p en t a flu or op h en yl)-3-(1,1,4,4-t et r a p h en ylb u t -1-
en yl)bor a n e. General procedure 1 was used to prepare this
compound from 1,1,4,4-tetraphenyl-1,3-butadiene (62.2 mg,
0.173 mmol) and 1 (60.0 mg, 0.173 mmol). 1H NMR: δ 7.37
(d, J ) 6.5 Hz, 2H, aromatic CH), 6.87-7.28 (m, 16H, aromatic
CH), 6.41 (d, J ) 7.2 Hz, 2H, aromatic CH), 6.28 (d, J ) 10.5
Hz, 1H, vinyl CH), 4.99 (dd, J ) 10.5, 11.2 Hz, 1H, BCH), 4.36
(d, 1H, CH). 13C NMR: δ 145.5, 141.7, 137.0, and 113.4 (C6F5),
154.4 (alkenyl Cquat), 143.6, 143.5, 142.2, and 138.7 (Cipso), 130.1
(alkenyl CH), 127.9, 127.9, 127.8, 127.6, 127.4, 127.2, 127.1,
127.0, 126.8, and 125.8, 125.8 (aromatic CH, others obscured
by solvent), 54.3 (CH), 48.3 (BCH). 19F NMR: δ -129.5 (d, J )
17.9 Hz, Fo), -150.0 (t, J ) 20.6 Hz, Fp), -161.7 (m, Fm). 11B
NMR: δ 13.5 (400).
â, deg
Rw2
GOF
V, Å3
CH3). 13C NMR: δ 147.7, 143.2, 137.7, and 114.1 (C6F5), 172.4
(dCH), 136.0 (BCH), 36.8 (dCHCH2), 29.9 and 22.5 (CH2), 13.8
(CH3). 19F NMR: δ -130.1 (dd, J ) 7.8 Hz and J ) 25.5 Hz,
Fo), -148.7 (tt, J ) 3.6 Hz and J ) 20.6 Hz, Fp), -161.5 (m,
Fm). 11B NMR: δ 58.1 (900).
Bis(p e n t a flu or op h e n yl)(t r a n s-2-p h e n yle t h e n yl)b o-
r a n e. General procedure 1 was used to prepare this compound
from phenylacetylene (15.7 µL, 0.143 mmol) and 1 (49.4 mg,
0.143 mmol). 1H NMR: d 7.51 (br m, 2H, vinyl CH); 7.34, 7.03
(m, 5H, C6H5). 13C NMR: δ 163.4 (dCH), 147.7, 143.2, 137.7,
and 114.0 (C6F5), 136.2 (Cipso), 132.2, 129.6, and 129.3 (C6H5),
131.9 (BCH). 19F NMR: δ -131.5 (dd, J ) 18.1 Hz and J )
6.4, Fo), -150.2 (t, J ) 21.3 Hz, Fp), -163.1 (m, Fm). 11B NMR:
δ 58.3 (770).
Eth yl 5-(Bis(pen taflu or oph en yl)bor yl)pen tan oate. Gen-
eral procedure 1 was used to prepare this compound from ethyl
4-pentenoate (17.0 mg, 0.082 mmol) and 1 (28.0 mg, 0.082
1
mmol). H NMR: δ 3.83 (q, J ) 7.2 Hz, 2H, OCH2), 1.86 (m,
2H, CH2CO), 1.57 (m, 2H, CH2), 1.40 (br m, 2H, BCH2), 1.07
(m, 2H, CH2), 0.70 (t, J ) 7.2 Hz, 3H, CH3). 13C NMR: δ 187.0
(CO), 149.2, 146.9, 137.8, and 119.7 (C6F5), 67.9 (CH2, OCH2),
34.1 (CH2CO), 26.4 and 24.0 (CH2), 21.2 (BCH2), 13.0 (CH3).
19F NMR: δ -134.5 (d, J ) 23.1 Hz, Fo), -158.1 (t, J ) 20.6
Hz, Fp), -163.8 (m, Fm). 11B NMR: δ 6.8 (360).
1,1-Bis(bis(p en ta flu or op h en yl)bor yl)-3,3-d im eth ylbu -
ta n e.51 General procedure 2 was used to prepare this known
compound from 3,3-dimethyl-1-butyne (5.3 µL, 0.043 mmol)
and 1 (30.0 mg, 0.086 mmol). 1H and 19F NMR data were
essentially identical to that reported in the literature. 13C
NMR: δ 145.96, 143.3, 137.7, and 113.8 (C6F5), 57.8 (CB2), 47.0
(CH2), 31.3 (CCH3), 29.1 (CCH3). 11B NMR: δ 70.0 (1500).
1,1-Bis(bis(p en ta flu or op h en yl)bor yl)h exa n e. General
procedure 2 was used to prepare this compound from 1-hexyne
Bis(p en t a flu or op h en yl)((Z)-1-m et h yl-1-p r op en yl)b o-
r a n e. Borane 1 (54.6 mg, 0.158 mmol) was loaded into a
sealable NMR tube, suspended in C6D6 (0.6 mL), and attached
to a vacuum line. The sample was degassed, and 2-butyne (86
Torr/34.2 mL, 0.087 mmol) was condensed into the tube, which
was then flame-sealed and warmed to room temperature. The
solution was shaken vigorously during which time the solid
dissolved, giving Z-CH3CHdC(CH3)B(C6F5)2 as the only prod-
uct. 1H NMR: δ 6.59 (q, J ) 6.8 Hz, 1H, CH), 1.64 (s, 3H,
C(B)CH3), 1.48 (d, 3H, C(H)CH3). 13C NMR: δ 161.8 (CH),
145.9, (CB), 146.2, 142.7, 137.5, and 114.3 (C6F5), 16.6 and 15.1
(CH3). 19F NMR: δ -133.0 (dd, J ) 12.2 and 24.4 Hz, Fo),
-151.6 (t, J ) 18.3 Hz, Fp), -163.1 (m, Fm). 11B NMR: δ 62.0
(640).
1
(9.0 µL, 0.078 mmol) and 1 (54.2 mg, 0.156 mmol). H NMR:
δ 3.55 (t, J ) 5.5 Hz, 1H, CHB2), 2.06 (dt, J ) 5.5 Hz and J )
7.4 Hz, 2H, CHCH2), 1.32, 1.13, 1.09 (m, 6H, CH2), 0.77 (t, J
) 7.1 Hz, 3H, CH3). 13C NMR: δ 148.5, 146.0, 138.8, and 111.9
(C6F5), 60.1 (CB2), 33.2 (CHCH2), 32.5, 31.1, and 22.6 (CH2),
13.8 (CH3). 19F NMR: δ -130.7 (d, J ) 17.1 Hz, Fo), -146.6 (t,
J ) 20.5 Hz, Fp), -160.1 (m, Fm). 11B NMR: δ 82.8 (400).
1,1-B i s (b i s (p e n t a flu o r o p h e n y l)b o r y l)-2-p h e n y l-
eth a n e. General procedure 2 was used to prepare this
compound from phenylacetylene (6.9 µL, 0.063 mmol) and 1
(43.6 mg, 0.126 mmol) in CD2Cl2 (0.6 mL). 1H NMR (CD2Cl2):δ
7.08-7.18 (m, 3H, aromatic CH), 6.86-6.91 (m, 2H, aromatic
CH), 4.18 (t, J ) 6.7 Hz, 1H, CHB2), 3.38 (d, 2H, CH2). 13C
NMR (C6D6): δ 146.2, 143.4, 137.6, and 113.6 (C6F5), 141.2
(Cipso), 131.9, 129.3, and 127.5 (C6H5), 59.1 (CB), 35.0 (CH2).
19F NMR (CD2Cl2): δ -130.3 (d, J ) 16.1 Hz, Fo), -147.7 (t, J
) 19.9 Hz, Fp), -160.9 (m, Fm). 11B NMR (CD2Cl2): δ 75.0
(1030).
E t h yl tr a n s-5-(Bis(p en t a flu or op h en yl)b or yl)-4-p en -
ten oa te. General procedure 1 was used to prepare this
compound from ethyl 4-pentynoate (11.0 mg, 0.087 mmol) and
1 (30.0 mg, 0.087 mmol). 1H NMR: δ 6.74 (m, J ) 17.4 Hz
and J ) 1.2 Hz, 1H, BCH), 6.49 (dt, J ) 5.7 Hz, 1H, dCH),
3.94 (q, J ) 7.1 Hz, 2H, OCH2), 2.28 (dt, J ) 6.7 Hz, 2H, d
CHCH2), 2.16 (t, 2H, CH2CO), 0.92 (t, 3H, CH3). 13C NMR: δ
174.1 (CO), 162.9 (dCH), 147.7, 142.8, 137.7, and 114.2 (C6F5),
136.5 (BC), 62.1 (OCH2), 32.2 and 31.3 (CH2), 13.9 (CH3). 19F
NMR: δ -130.3 (dd, J ) 9.4 Hz and J ) 23.5 Hz, Fo), -149.2
(t, J ) 19.8 Hz, Fp), -161.5 (m, Fm). 11B NMR: δ 51.7 (1155).
X-r a y Cr ysta llogr a p h y. Measurements were made on a
Bruker AXS SMART CCD area-detector diffractometer using
graphite-monochromated Mo KR radiation (λ ) 0.71073 Å).
The structures was solved by direct methods and refined on
F2 values by full-matrix least-squares for all unique data. Table
Bis(p en t a flu or op h en yl)((Z)-1,2-d ip h en ylet h en yl)b o-
r a n e. General procedure 1 was used to prepare this compound
from diphenylacetylene (20.1 mg, 0.113 mmol) and 1 (39.0 mg,
1
0.113 mmol). H NMR: δ 7.62 (s, 1H, vinyl CH), 7.09 (d, J )
7.3 Hz, 2H, Ho), 7.02 (d, J ) 7.0 Hz, 2H, Ho), 6.98 (t, J ) 7.3
Hz, 2H, H), 6.91 (t, J ) 7.0 Hz, 1H, Hp), 6.86 (t, J ) 7.3 Hz,
1H, Hp), 6.80 (t, J ) 7.0 Hz, 2H, Hm). 13C NMR: δ 146.3, 142.9,
137.7, and 114.7 (C6F5), 157.8 (CH), 150.6 (BC), 141.2 and
135.5 (Cipso), 132.1, 131.2, 129.2, 128.7, 128.6, and 127.6
(aromatic CH). 19F NMR: δ -132.3 (dd, J ) 6.1 Hz and J )
24.4 Hz, Fo), -150.7 (t, J ) 19.8 Hz, Fp), -162.9 (m, Fm). 11B
NMR: δ 65.1 (770).
Bis(p en ta flu or op h en yl)(tr a n s-3,3-d im eth yl-1-bu ten yl)-
bor a n e. General procedure 1 was used to prepare this
compound from 3,3-dimethyl-1-butyne (5.3 µL, 0.043 mmol)
1
and 1 (15.0 mg, 0.043 mmol). H NMR: 6.95, 6.81 (ABq, J )
17.6 Hz, 2H, vinyl CH), 0.93 (s, 9H, CH3). 13C NMR: δ 180.4
(dCH), 147.7, 143.3, 137.6, and 114.0 (C6F5), 130.1 (BCH), 36.5
(CCH3), 28.1 (CCH3). 19F NMR: δ -130.0 (dd, J ) 7.6 Hz and
J ) 25.7 Hz, Fo), -148.4 (tt, J ) 4.1 Hz and J ) 20.6 Hz, Fp),
-161.4 (m, Fm). 11B NMR: δ 58.6 (960).
Bis(p en ta flu or op h en yl)(tr a n s-1-h exen yl)bor a n e. Gen-
eral procedure 1 was used to prepare this compound from
1-hexyne (9.0 µL, 0.078 mmol) and 1 (27.1 mg, 0.078 mmol).
1H NMR: δ 6.83 (br m, 2H, vinyl CH), 2.07 (m, 2H, dCHCH2),
1.24 (m, 2H, CH2), 1.17 (m, 2H, CH2), 0.79 (t, J ) 7.2 Hz, 3H,
(58) Sheldrick, G. M. SHELXTL, version 5; Bruker AXS Inc.:
Madison, WI, 1994.