Organobismuth(III) and organobismuth(V) complexes containing pyridyl and amino functional groups. Syntheses and characterizations of BiIIIAr3 (Ar = p-C6H4(NMe2), p-C6H4CH2(NPri2), p-C6H4[CH2N(2-Py)2]),

Article abstract of DOI:10.1021/om960641w

The synthesis of tertiary bismuth(III) complexes containing amino or pyridyl functional groups has been investigated. An improved synthesis for Bi[p-C₆H₄(NMe₂)]₃ (1) has been achieved. Two new complexes, Bi[p-C₆H₄CH₂(NPrⁱ₂)] ₃ (2) and Bi[p-C₆H₄CH₂N(2-Py)₂]₃ (3), have been obtained. The bismuth(V) derivatives of compounds 1 and 3 have been synthesized via chlorine oxidation of 1 and 3 and the subsequent substitution reactions. Compounds Bi[p-C₆H₄(NMe₂)]₃(O ₂CCF₃)₂ (5) and Bi{p-C₆H₄[CH₂N(2-Py₂)]} ₃(O₂CCH₃)₂ (7) were obtained from the reactions of the corresponding dichloride complexes, BiAr₃Cl₂, with the appropriate silver salt. NMR spectroscopic studies established that in solution, compound 5 is fluxional while compound 7 is rigid. A dinuclear complex Bi₂[p-C₆H₄(NMe₂)]₆Cl ₂(O) (6) was isolated as the major product when the dichloride complex Bi[p-C₆H₄(NMe₂)]₃Cl₂ was reacted with NaOH in nondistilled reagent grade dichloromethane. A quaternary bismuth(V) complex, Bi[p-C₆H₄(NMe₂)]₄[PF₆] (8), was obtained in good yield when Bi[p-C₆H₄(NMe₂)]₃Cl₂ was reacted with TlPF₆ in a 1:2 ratio. A closely related quaternary bismuth(V) complex {Bi[p-C₆H₄(NMe₂)]₄} ₂[Ag₂Cl₄] (9), which contains an unusual three-coordinate dinuclear anion Ag₂Cl₄^2-, was obtained as a trace product from the reactions of Bi[p-C₆H₄(NMe₂)]₃Cl₂ with silver salts. The crystal structures of compounds 1 and 5-9 were determined by single-crystal X-ray diffraction analyses.

Full text of DOI:10.1021/om960641w

Organometallics 1996, 15, 5613-5621
5613
Or ga n obism u th (III) a n d Or ga n obism u th (V) Com p lexes
Con ta in in g P yr id yl a n d Am in o F u n ction a l Gr ou p s.
Syn th eses a n d Ch a r a cter iza tion s of BiIIIAr 3 (Ar )
p-C6H4(NMe2), p-C6H4CH2(NP r i ), p-C6H4[CH2N(2-P y)2]),
2
BiVAr 3L2, [BiVAr 3Cl]2O, [BiVAr 4][P F 6], a n d
[BiVAr 4]2[Ag2Cl4] (Ar ) p-C6H4(NMe2) or
-
-
p-C6H4[CH2N(2-P y)2], L ) Cl, CH3CO2 , CF 3CO2 )
Abdi Hassan, Steven R. Breeze, Silke Courtenay, Chris Deslippe, and
Suning Wang*
Department of Chemistry, Queen’s University, Kingston, Ontario, Canada K7L 3N6
Received J uly 31, 1996X
The synthesis of tertiary bismuth(III) complexes containing amino or pyridyl functional
groups has been investigated. An improved synthesis for Bi[p-C6H4(NMe2)]3 (1) has been
achieved. Two new complexes, Bi[p-C6H4CH2(NPri )]3 (2) and Bi[p-C6H4CH2N(2-Py)2]3 (3),
2
have been obtained. The bismuth(V) derivatives of compounds 1 and 3 have been synthesized
via chlorine oxidation of 1 and 3 and the subsequent substitution reactions. Compounds
Bi[p-C6H4(NMe2)]3(O2CCF3)2 (5) and Bi{p-C6H4[CH2N(2-Py2)]}3(O2CCH3)2 (7) were obtained
from the reactions of the corresponding dichloride complexes, BiAr3Cl2, with the appropriate
silver salt. NMR spectroscopic studies established that in solution, compound 5 is fluxional
while compound 7 is rigid. A dinuclear complex Bi2[p-C6H4(NMe2)]6Cl2(O) (6) was isolated
as the major product when the dichloride complex Bi[p-C6H4(NMe2)]3Cl2 was reacted with
NaOH in nondistilled reagent grade dichloromethane. A quaternary bismuth(V) complex,
Bi[p-C6H4(NMe2)]4[PF6] (8), was obtained in good yield when Bi[p-C6H4(NMe2)]3Cl2 was
reacted with TlPF6 in a 1:2 ratio. A closely related quaternary bismuth(V) complex {Bi[p-
C6H4(NMe2)]4}2[Ag2Cl4] (9), which contains an unusual three-coordinate dinuclear anion
Ag2Cl42-, was obtained as a trace product from the reactions of Bi[p-C6H4(NMe2)]3Cl2 with
silver salts. The crystal structures of compounds 1 and 5-9 were determined by single-
crystal X-ray diffraction analyses.
In tr od u ction
BiAr3, and triarylbismuth(V) complexes, BiAr3X2 (X )
halide or carbonate), containing an -OR or -NO2 group
are known,1a,g,j triarylbismuth(III) and triarylbismuth(V)
complexes containing amino or pyridyl donor functional
groups are still scarce. The only previously known
example of BiAr3 complexes containing an amino func-
tional group is Bi[p-C6H4(NMe2)]3 (1), reported some 45
years ago by Gilman and Yablunky.2 The yield of
compound 1 reported in the original synthesis was poor,
and the chemistry and structure of 1 have hardly been
investigated. We therefore decided to reinvestigate the
synthesis and chemistry of compound 1. In addition,
we have explored the syntheses of new BiAr3 complexes
containing amino or pyridyl functional groups. Two new
There has been much interest in bismuth compounds
due to their various applications in medicines, catalysis,
and materials.1 The exploration and information on the
chemistry of organobismuth complexes are still very
limited. We have been interested in the syntheses of
bismuth complexes containing functional groups such
as pyridyl and hydroxo because of their potential use
as precursors for the formation of polynuclear mixed
metal complexes, e.g., BiCu complexes. Our effort has
focused on two types of organobismuth complexes,
bismuth(III) complexes, BiAr3, and bismuth(V) com-
plexes, BiAr3L2, where Ar is a phenyl derivative con-
taining a donor functional group such as amino or
pyridyl. Although a few triarylbismuth(III) complexes,
complexes, Bi[p-C6H4CH2(NPri )]3 (2) and Bi{p-C6H4-
2
[CH2N(2-Py)2]}3 (3), have been obtained. Several in-
teresting bismuth(V) complexes derived from com-
pounds 1 and 3 have been characterized. The details
are presented herein.
X Abstract published in Advance ACS Abstracts, November 15, 1996.
(1) (a) Freedman, L. D.; Doak, G. O. Chem. Rev. 1982, 82, 15. (b)
Herman, W. A.; Herdtweck, E.; Pajdla, L. Inorg. Chem. 1991, 30, 2579.
(c) Metal-based Anti-tumor Drugs; Gielen, M. F., Ed.; Freund Publish-
ing House: London, 1988. (d) Barton, D. H. R.; Charpiot, B.; Dau, E.
T. H.; Motherwell, W. B.; Pascard, C. Helv. Chim. Acta 1984, 67, 586.
(e) Massiani, M. C.; Papiernik, R.; Hubert-Pfalzgraf, L. G.; Daran J .
C. J . Chem. Soc., Chem. Commun. 1990, 301. (f) J ones, C. M.; Burkart,
M. D.; Bachman, R. E.; Serra, D. L.; Hwu, S. J .; Whitmire, K. H. Inorg.
Chem. 1993, 32, 5136. (g) Matano, Y.; Miyamatsu, T.; Suzuki, H.
Organometallics 1996, 15, 1951. (h) Mantano, Y.; Kinoshita, M.;
Suzuki, H. Bull. Chem. Soc. J pn. 1992, 65, 3504. (i) Suzuki, H.;
Murafuji, T. J . Chem. Soc., Chem. Commun. 1992, 1143. (j) Barton,
D. H. R.; Bhatnagar, N. Y.; Finet, J . P.; Motherwell, W. B. Tetrahedron
1986, 42, 3111.
Exp er im en ta l Section
All reactions were performed by using the Schlenk vacuum
line techniques under a nitrogen atmosphere. All solvents
were freshly distilled over the appropriate drying reagents
(2) Gilman, H.; Yablunky, H. L. J . Am. Chem. Soc. 1941, 63, 207.
S0276-7333(96)00641-3 CCC: $12.00 © 1996 American Chemical Society

5614 Organometallics, Vol. 15, No. 26, 1996
Hassan et al.
prior to use, unless specified otherwise. BiCl3, Ag(O2CCH3),
Ag(O2CCF3), TlPF6, 4-bromo-N,N-dimethylaniline, 4-bromoben-
zyl bromide, n-butyllithium, di-2-pyridylamine, 4-bromo-N,N-
diisopropylbenzylamine, and trifluoroacetic acid were pur-
chased from Aldrich Chemical Co. Bis(2-pyridylmethyl)amine
was synthesized by a modified procedure reported in litera-
ture.3 PhI‚Cl2 was prepared by the reaction of phenyl iodide
with chlorine gas in diethyl ether. NMR spectra were recorded
on a Bru¨ker AC 300 spectrometer. Elemental analyses were
performed by Canadian Microanalytical Service, Delta, BC.
P r ep a r a t ion of (4-Br om ob en zyl)d i-2-p yr id yla m in e.
4-Bromobenzyl bromide (8 g, 32 mmol), di-2-pyridylamine (5
g, 29 mmol), and sodium hydroxide pellets (approximately 10
g) were mixed in a 1 L flask containing 300 mL of reagent
grade THF. The mixture was refluxed for 5 h and stirred for
an additional 16 h at 23 °C. The solution was then filtered
and evaporated to dryness. Water was added to the residue.
The product was extracted with several portions of diethyl
ether. After the diethyl ether solution was concentrated, the
product was obtained by crystallization at 0 °C in 62% yield.
Mp 95 °C. Anal. Calcd for BrC17H14N3: C, 60.02; H, 4.12; N,
12.35. Found: C, 59.92; H, 4.17; N, 12.34. 1H NMR (δ, ppm,
CDCl3): 5.42 (s, 2H, CH2), 6.83 (m, 2H, Py), 7.13, 7.34 (AA′BB′,
2H, 2H, phenyl, J AB ) 8.4 Hz), 7.23 (d, 2H, Py), 7.48 (m, 2H,
Py), 8.30 (m, 2H, Py). 13C NMR (δ, ppm, CDCl3): 50.78 (CH2),
114.55, 117.42, 120.46, 129.22, 131.43, 137.35, 138.74, 148.47,
157.02 (aromatic). MS: 340 (molecular ion).
Bi[p-C6H4CH2(NP r i2)]3 (2). The colorless compound 2 was
crystallized from acetonitrile. Yield 43%. Mp 85 °C, dec.
Anal. Calcd for BiC39H60N3: C, 60.08; H, 7.70; N, 5.39.
Found: C, 59.71; H, 7.80; N, 5.42. 1H NMR (δ, ppm, CDCl3):
3
0.98 (d, 6H, CH3, J ) 6.6 Hz), 2.98 (septet, 1H, CH), 3.58 (s,
2H, CH2), 7.36, 7.63 (AA′BB′′, 2H, 2H, J AB ) 7.8 Hz, phenyl).
13C NMR (δ, ppm, CDCl3): 20.89 (CH3), 47.79 (CH), 49.00
(CH2), 130.12, 137.37, 142.79, 152.07 (phenyl).
Bi[p-C6H4CH2N(2-P y)2]3 (3). The colorless crystals of
compound 3 were obtained by crystallization in acetonitrile.
Yield 15%. Mp 115-120 °C, dec. Anal. Calcd for BiC51
-
H
42N9: C, 61.88; H, 4.28; N, 12.73. Found: C, 61.13; H, 4.22;
N, 12.60. 1H NMR (δ, ppm, CDCl3): 5.43 (s, 2H, CH2), 6.82
(m, 2H, Py), 7.12, 7.27 (AA′BB′, 2H, 2H, phenyl, J AB ) 8.1 Hz),
7.49 (m, 4H, Py), 8.28 (m, 2H, Py). 13C NMR (δ, ppm, CDCl3):
51.56 (CH3), 114.71, 117.29, 148.19, 157.12 (pyridyl), 129.17,
138.87, 152.72 (phenyl), 137.41, 137.67 (pyridyl, phenyl).
P r ep a r a tion of Bi[p-C6H4(NMe2)]3Cl2 (4). A 0.100 g
(0.176 mmol) sample of compound 1 was dissolved in 20 mL
of CH2Cl2. The solution was cooled to -78 °C by using a dry
ice/acetone bath. PhI‚Cl2 (0.058 g, 0.211 mmol) was added.
The mixture was stirred for 3 h and was allowed to warm up
to 23 °C. The solvent and phenyl iodide were removed in
vacuo. The residue was redissolved in CH2Cl2. Concentration
of the solution yielded orange crystals of compound 4 in 88%
yield. Compound 4 cocrystallizes with the CH2Cl2 solvent
molecule. Anal. Calcd for the vacuum dried sample, BiCl2C24
-
H
30N3: C, 45.00; H, 4.69; N, 4.65. Found: C, 44.02; H, 4.65;
(4-Br om oben zyl)bis(2-pyr idylm eth yl)am in e. The ligand
was prepared by the same procedure as above. The resulting
oily compound was purified by distillation under vacuum (250
°C, 0.02 mmHg). The purified ligand is a yellowish orange
oil. Anal. Calcd for BrC19H18N3: C, 61.97; H, 4.89; N, 11.42.
Found: C, 60.91; H, 5.05; N, 11.06. The poor agreement of
carbon and nitrogen content with the calculated value is
believed to be caused by impurities, such as water, since it
has a high affinity to water via hydrogen bonds. 1H NMR (δ,
ppm, CDCl3): 3.59 (s, 2H, CH2), 3.75 (s, 4H, CH2), 7.09 (m,
2H, Py), 7.24, 7.38 (AA′BB′, 2H, 2H, phenyl, J AB ) 8.4 Hz),
7.49 (d, 2H, Py), 7.60 (m, 2H, Py), 8.47 (m, 2H, Py). 13C NMR
(δ, ppm, CDCl3): 57.77 (CH2), 59.93 (CH2), 120.84, 122.05,
122.85, 130.58, 131.40, 136.47, 138.03, 149.06, 159.43 (aro-
matic). MS: 368 (molecular ion).
Gen er a l P r oced u r e for th e Syn th esis of BiAr 3 Com -
p lexes. The BiAr3 complexes were obtained by a modified
literature procedure.2 The synthesis of Bi[p-C6H4(NMe2)2]3
given below represents the typical procedure and reaction
conditions employed for the BiAr3 complexes described in this
report. The experimental details for the synthesis of other
BiAr3 complexes are therefore omitted.
P r ep a r a tion of Bi[p-C6H4(NMe2)]3 (1). A 1.00 g (5.00
mmol) sample of 4-bromo-N,N′-dimethylaniline was dissolved
in 20 mL of THF. This solution was then cooled to -78 °C by
using a dry ice/acetone bath. n-Butyllithium (3.12 mL of 1.6
M, 1.60 mmol) in hexane was added. After the solution was
stirred for 30 min at -78 °C, a 0.500 g, (1.59 mmol) sample of
BiCl3 dissolved in 10 mL of THF was added. The mixture was
stirred for 1 h at -78 °C and was allowed to warm up to 23
°C. After being stirred for an additional 12 h, the THF solvent
was removed in vacuo and the residue was extracted with 20
mL of toluene. The toluene extract was filtered and concen-
trated to about 10 mL. After the solution was allowed to stand
at 0 °C for a few days, colorless crystals of 1 were obtained
(0.96 g, yield 86%). More crystals can be isolated by further
concentrating the mother liquor. Mp 200 °C, dec. Anal. Calcd
for BiC24H30H3: C, 50.62; H, 5.31; N, 7.38. Found: C, 50.76;
H, 5.18; N, 7.30. 1H NMR (δ, ppm, CDCl3): 2.91 (s, 6H, CH3),
6.72, 7.57 (AA′BB′′, 2H, 2H, J AB ) 8.1 Hz, phenyl). 13C NMR
(δ, ppm, CDCl3): 51.85 (CH3), 130.78, 136.89, 144.99, 151.37
(phenyl).
N, 6.30. The low observed carbon and nitrogen content can
be attributed to the presence of 0.20 CH2Cl2 per molecule of 4
(calcd for BiCl2C24H30N3/0.2 CH2Cl2: C, 44.21; H, 4.63; N, 6.39).
1H NMR (δ, ppm, CDCl3): 3.01 (s, 6H, CH3), 7.78, 8.24 (AA′BB′,
2H, 2H, phenyl, J AB ) 9.3 Hz).
Bi[p-C6H4CH2N(2-Py)2]3Cl2 was obtained by the same pro-
cedure in 74% yield.
P r ep a r a tion of Bi[p-C6H4(NMe2)]3(O2CCF 3)2 (5). Silver
trifluoroacetate (0.083 g, 0.375 mmol) was added to a 20 mL
THF solution containing 0.120 g (0.186 mmol) of compound 4.
The reaction mixture was stirred for 17 h at 23 °C. The
solution was filtered and concentrated in vacuo. Orange
crystals of compound 5 were obtained at 0 °C in 71% yield.
Mp 120 °C. Anal. Calcd for C28H30N3BiO4F6: C, 42.25; H,
3.77; N, 5.28. Found: C, 42.24; H, 3.80; N, 5.42. 1H NMR (δ,
ppm, CDCl3): 3.01 (s, 6H, CH3), 6.83, 7.89 (AA′BB′, 2H, 2H,
phenyl, J AB ) 8.8 Hz).
P r ep a r a tion of Bi2[p-C6H4(NMe2)]6Cl2(O) (6). A 0.100
g (0.156 mmol) sample of compound 4 was dissolved in 20 mL
of reagent grade dichloromethane in the presence of 1.5 equiv
of NaOH (5 mg). This solution was stirred for 3 h and filtered.
The filtrate was concentrated to about 4 mL and kept at 0 °C.
After a few days, yellow crystals of compound 6 were obtained
in 35% yield. Mp 159 °C, dec. Compound 6 cocrystallizes with
one H2O and one CH2Cl2 solvent molecule. Anal. Calcd for
the CH2Cl2 free sample, C49H62Bi2ON6Cl2/H2O: C, 46.30; H,
5.14; N, 6.75. Found: C, 45.67; H, 5.26; N, 6.80. 1H NMR (δ,
ppm, CDCl3): 3.01 (s, 6H, CH3), 6.81, 8.19 (AA′BB′, 2H, 2H,
phenyl, J AB ) 9.1 Hz).
P r ep a r a tion of Bi[p-C6H4CH2N(2-P y)2]3(O2CCH3)2 (7).
A sample of 80 mg (0.075 mmol) of Bi[p-C6H4CH2N(2-Py)2]3-
Cl2 was dissolved in 10 mL of THF. Ag(O2CCH3) (25 mg, 0.151
mmol) was added to the solution. The mixture was stirred
for 16 h at 23 °C. The solution was filtered and concentrated
to about 4 mL. Hexane (0.5 mL) was added. After being
allowed to stand a few days at 0 °C, colorless crystals of
compound 7 were obtained (89 mg, 80% yield). Compound 7
cocrystallizes with two THF solvent molecules. Mp 95-97 °C.
Anal. Calcd for the vacuum dried sample, C55H54N9BiO4: C,
59.62; H, 4.73; N, 11.33. Found: C, 59.19; H, 4.83; N, 10.40.
1H NMR (δ, ppm, CDCl3, 296 K): 1.71 (s, 6H, CH3), 5.49, 5.51
(s, 6H, CH2), 6.83, 7.15, 7.50, 7.92, 8.02, 8.29 (m, 36H,
aromatic). 13C NMR (δ, ppm, CDCl3, 296 K): 29.80 (CH3),
50.89, 50.97, 51.08 (CH2), 114.48, 117.48, 137.40, 148.47,
(3) Romary, J . K.; Zachariasen, R. D.; Barger, J . D.; Schiesser, H.
J . Chem. Soc. C 1968, 2884.

Organobismuth(III) and Organobismuth(V) Complexes
Organometallics, Vol. 15, No. 26, 1996 5615
Ta ble 1. Cr ysta llogr a p h ic Da ta
1
5
6
7
8
9
formula
fw
space group
a, Å
b, Å
c, Å
C
24H30N3Bi
C28H30N3O4F6Bi C49H64N6O2Cl4Bi2 C63H64N9O6Bi
C32H40N4F6PBi
834.64
P21/n
15.864(5)
12.789(7)
15.975(6)
90
90.59(3)
90
3240(2)
4
C32H40N4Cl2AgBi
868.45
C2/c
26.789(9)
17.534(3)
18.144(5)
90
127.47
90
569.50
P1h
795.53
C2/c
12.427(6)
12.461(8)
19.616(4)
90
1328.86
P21/n
13.219(5)
19.875(6)
21.043(8)
90
1252.24
P21/n
8.743(3)
38.33(1)
17.744(4)
90
11.478(4)
11.495(3)
11.394(4)
103.38(3)
110.43(3)
111.82(3)
1189.9(9)
2
R, deg
â, deg
99.14(2)
90
103.17(3)
90
101.90(3)
90
γ, deg
V, Å3
2999(2)
4
5383(3)
4
5818(2)
4
6764(3)
8
1.71
Z
D, g cm-3
T, °C
1.59
23
1.76
1.64
1.43
1.71
0
23
23
23
23
radiation, λ, Å
Mo KR, 0.710 69 Mo KR, 0.710 69 Mo KR, 0.710 69
Mo KR, 0.710 69 Ag KR, 0.560 83
Mo KR, 0.710 69
µ, cm-1
73.98
0.21-1.00
50
59.43
0.81-1.00
50
67.57
0.89-1.00
50
30.83
0.90-1.00
45
22.33
0.65-0.89
40
59.47
trans. coeff.
2θmax, deg
reflns measured
reflns observed
no. of variables
0.85-1.00
45
3335
4204
2786
7778
7519
6120
I > 3.00σ(I), 2297 I > 2.70σ(I), 803 I > 1.80σ(I), 2224 I > 2.30σ(I), 2075 I > 3.00σ(I), 2904 I > 2.70σ(I), 1142
253
126
318
322
397
181
largest shift/esd in final cycle 0.00
largest electron density peak, 1.61
e-/Å3
0.00
1.34
0.01
1.29
0.01
1.12
0.00
0.61
0.00
0.50
Ra
0.047
0.044
1.64
0.058
0.051
1.39
0.076
0.064
1.48
0.064
0.062
1.28
0.027
0.023
1.09
0.043
0.036
1.21
b
Rw
goodness of fitc
a
b
2
R ) ∑|Fo| - |Fc|/∑|Fo|. Rw ) (∑w(|Fo| - |Fc|)2/∑wFo
)
-1/2, w ) 1/σ2(Fo). c S ) ∑(|Fo| - |Fc|)/σ(No - Nv).
156.85 (pyridyl), 129.74, 130.20, 130.38, (CH, phenyl), 133.65,
133.89, 134.38 (CH, phenyl), 142.51, 143.27, 143.82 (C, phenyl),
154.17, 155.95, 159.09 (phenyl, the carbon atom bonded to
bismuth).
crystals. Neutral atom scattering factors were taken from
Cromer and Waber.5
The crystal of 1 belongs to the triclinic space group P1h. The
crystals of 6-8 belong to the monoclinic space group P21/n,
uniquely determined by the systematic absences (0k0, k ) 2n
+ 1; h0l, h + l ) 2n + 1) while the crystals of 5 and 9 belong
to the monoclinic space group C2/c, determined by the sys-
tematic absences (hkl, h + k ) 2n + 1; h0l, l ) 2n + 1) and
the successful structural solution and refinement. The posi-
tions of the metal atoms in all structures were determined
either by the heavy atom method or by direct methods. Non-
hydrogen atoms were located by subsequent difference Fourier
syntheses. A THF solvent molecule and a H2O molecule
located in the lattice of compound 6 were refined successfully.
Two THF solvent molecules, co-crystallized with compound 7,
were located in the lattice. Both solvent molecules show some
degree of disorder, which could not be modeled successfully
due to the limitation of the data. All non-hydrogen atoms in
1 and 8 were refined anisotropically. Due to the lack of a
sufficient number of reflections, only bismuth, fluorine, oxygen,
nitrogen, and one carbon atom in 5, bismuth, chlorine, oxygen,
and nitrogen atoms in 6, bismuth in 7, and bismuth, silver,
and chlorine atoms in 9 were refined anisotropically. The
positions of the hydrogen atoms were calculated wherever
possible and their contributions were included in the structural
factor calculation. Further details of the crystallographic
analyses can be found in Table 1.
P r ep a r a tion of Bi[p-C6H4(NMe2)]4[P F 6] (8). A 0.100 g,
(0.156 mmol) sample of compound 4 was dissolved in 20 mL
of CH2Cl2 at 23 °C. TlPF6 (0.110 g, 0.312 mmol) was added to
the solution. The mixture was stirred for 16 h. The solution
was then filtered and concentrated to about 4 mL. After the
addition of 2 mL of hexane and allowing the solution to stand
at 0 °C for a few days, green crystals of compound 8 were
obtained (117 mg, 90% yield). Mp 140 °C, dec. Anal. Calcd
for C32H40N4BiPF6: C, 46.04; H, 4.79; N, 6.71. Found: C,
45.97; H, 4.57; N, 6.70. 1H NMR (δ, ppm, CD2Cl2, 180 K): 2.98
(s, 6H, CH3), 6.78 (d, 2H, J ) 8.4 Hz, phenyl), 7.38 (broad,
2H, phenyl). 13C NMR (δ, ppm, CD2Cl2, 180 K): 39.81 (CH3),
113.34, 116.33, 135.83, 151.24 (aromatic).
Bi[p-C6H4(NMe2)]4[AgCl2] (9). This compound was ob-
tained as a trace yellow crystalline product from the reactions
of compound 4 with silver salts, such as Ag(O2CCF3). Inde-
pendent synthesis for this compound has not yet been achieved.
Its poor solubility in common organic solvents, such as CD2Cl2,
THF, and acetone, prevented us from taking NMR spectra.
The elemental analysis was not performed due to the lack of
a sufficient amount of sample. Mp 178 °C, dec.
X-r a y Diffr a ction An a lyses. The crystals of compound 1
were obtained from a concentrated toluene solution at 0 °C,
while the crystals of 5-9 were obtained from the mixed
solvents of CH2Cl2/hexane or THF/hexane at 0 °C. They were
mounted on glass fibers and sealed with epoxy glue. Data
were collected at 23 °C on a Rigaku AFC6S diffractometer with
graphite-monochromated Mo KR radiation for compounds 1,
5-7, and 9. The data for compound 8 were collected at -79
°C on a Siemens P3 diffractometer with a graphite-monochro-
mated Ag KR radiation. All data were processed on a Silicon
Graphics computer using the TEXSAN crystallographic soft-
ware package4 and corrected for decay and Lorentz-polariza-
tion effects. An empirical absorption correction based on
azimuthal scans of several reflections was applied to all
Resu lts a n d Discu ssion
Syn th eses a n d Str u ctu r es of Ter tia r y Bism u th -
(III) Com p lexes, BiIII[p-C6H4(NMe2)]3 (1), BiIII[p-
C6H4(CH2NP r i )]3 (2), an d BiIII[p-C6H4CH2N(2-P y)2]3
2
(3). Most of the previously investigated organobis-
muth(III) complexes involve simple aromatic or aliphatic
ligands. Compound 1 is the only known example of a
tertiary aromatic bismuth(III) complex containing an
amino functional group. Although the synthesis of
compound 1 was reported many years ago, its crystal
structure has not been reported. In addition, perhaps
(5) Cromer, D. T.; Waber, J . T. International Tables for X-ray
Crystallography; Kynoch Press: Birmingham, Al, 1974; Vol. 4, Table
2.2A.
(4) TEXSAN-TEXRAY Structure Analysis Package, Molecular Struc-
ture Corporation, Houston, TX, 1985 and 1992.

5616 Organometallics, Vol. 15, No. 26, 1996
Hassan et al.
due to the poor yield reported in the original synthesis,
the chemistry involving this compound has been hardly
investigated. We therefore conducted the investigation
on an improved synthetic method for compound 1 and
its solid state structure. By modifying a previously
reported procedure2 for compound 1, we have been able
to obtain this compound in very good yield from the
reaction of BiCl3 with Li(p-C6H4NMe2) in an approxi-
mate 1:3 ratio. The structure of compound 1 has been
determined by a single-crystal X-ray diffraction analy-
sis. Important bond lengths and angles for 1 are listed
in Table 2. As shown in Figure 1, compound 1 has a
pyramidal geometry, resembling that of BiPh3. The
Bi-C bond lengths (2.22(2)-2.25(2) Å) and C-Bi-C
angles (93.7(6)-95.6(5)°) are very similar to those
observed6 in BiPh3. One notable feature of compound
1 is the conjugation of the nitrogen lone pair with the
phenyl ring, as indicated by the planar geometry of the
nitrogen atom (the sum of the angles surrounding each
nitrogen atom is nearly 360°) and the short bond
distance between the nitrogen atom and the carbon
atom of the phenyl ring (1.36(2)-1.41(2) Å). The lone
pair conjugation is not a desirable feature for the
bismuth complex because it will make the coordination
of the nitrogen atom to a metal center, such as a
copper(II) ion, difficult.
significantly from those of the anticipated product,
Bi[p-C6H4CH2N(2-Py)2CuCl2]3. The composition of the
green compound still remains unknown.
We have not been able to convert the bbdpma to the
corresponding lithium salt, which is attributed to the
high reactivity of the methylene protons in the bbdpma
ligand toward n-butyllithium. The attempted synthesis
of the corresponding bismuth(III) complex was therefore
unsuccessful.
Syn th eses a n d Str u ctu r es of Bi[p-C6H4(NMe2)]3-
(O2CCF 3)2 (5), Bi2[p-C6H4(NMe2)]6Cl2(O) (6), a n d
Bi[p-C6H4CH2N(2-P y)2]3(O2CCH3)2 (7). It has been
established earlier that tertiary aromatic bismuth(III)
complexes undergo oxidative addition reactions readily
with halogens, such as the chlorine molecule,1a,8 to form
the bismuth(V) complex BiVAr3X2, which is a good
starting material for the synthesis of new bismuth(V)
derivatives. We therefore performed the oxidation
reactions of compounds 1-3 by using the chlorine
delivery reagent, PhI‚Cl2. At -78 °C, both compounds
1 and 3 can be oxidized cleanly to form the correspond-
ing dichloride products, Bi[p-C6H4(NMe2)]3Cl2 and Bi[p-
C6H4CH2N(2-Py)2]3Cl2, respectively, while the reaction
of compound 2 with PhI‚Cl2 appeared to generate
several products which have not been isolated at this
time. The Bi[p-C6H4(NMe2)]3Cl2 complex was reported8
by Keck and Klar in 1972. The structure of this
compound, however, has not been determined. The
crystal structure of the analogous complex BiPh3Cl2 has
been reported earlier to be a distorted trigonal bipyra-
mid.9 Our preliminary X-ray diffraction analysis re-
sults10 for the Bi[p-C6H4(NMe2)]3Cl2 complex revealed
that this compound has a trigonal bipyramidal geometry
with the bismuth and the two chlorine atoms lying on
the crystallographically imposed C3 axis. The two Bi-
Cl bond lengths, 2.46(3) and 2.73(3) Å, are significantly
different, but the average 2.59 Å bond length is com-
parable to that found in BiPh3Cl2. The Bi-C bond
length of 2.20(2) Å is similar to that found in compound
of 1. The C-Bi-Cl angles range from 84.8(9)° to
95.2(9)°, similar to those observed in the BiPh3Cl2
compound. Molecular modeling showed that the struc-
ture of Bi[p-C6H4CH2N(2-Py)2]3Cl2 resembles those of
BiPh3Cl2 and Bi[p-C6H4(NMe2)]3Cl2 (4). We therefore
did not conduct the X-ray diffraction analysis for this
compound.
To prevent the conjugation of the lone pair, we
synthesized compound 2, BiIII(p-C6H4CH2NPri ) , where
2 3
the amino group is separated from the phenyl ring by a
methylene group, from the reaction of BiCl3 with 3 equiv
of Li(p-C6H4CH2NPri ). Compound 2 was characterized
2
by NMR spectroscopic and elemental analyses. The lack
of suitable single crystals for X-ray diffraction analysis
prevented the crystal structural determination, but we
believe that the structure of 2 is similar to that of 1 and
BiPh3.
To further increase the versatility of the tertiary
aromatic bismuth(III) complexes containing functional
groups, we synthesized the chelating ligands, (4-bro-
mobenzyl)di-2-pyridylamine (bbdpa) and (4-bromoben-
zyl)bis(2-pyridylmethyl)amine (bbdpma). The bbdpa
and bbdpma ligands were obtained from the reactions
of the corresponding secondary amines with 4-bro-
mobenzyl bromide by utilizing the reactivity difference
of the two bromo sites, as shown in Scheme 1. We have
been able to convert the bbdpa ligand to the correspond-
ing lithium salt, Li[p-C6H4CH2N(2-Py)2], by the reaction
of n-butyllithium with bbdpa at -78 °C. The subse-
quent reaction of Li[p-C6H4CH2N(2-Py)2] with BiCl3
yielded compound 3, BiIII[p-C6H4CH2N(2-Py)2]3, which
was characterized by elemental and NMR spectroscopic
analyses. The crystal structure of compound 3 has not
been determined due to the lack of single crystals.
Molecular modeling,7 however, showed that the basic
structural features of compound 3 should be similar to
that of 1. Compound 3 is the first example of a tertiary
organobismuth(III) complex containing a chelating func-
tional group. We examined the utility of the chelating
group of compound 3 in binding to a metal center by
performing the reaction of compound 3 with 3 equiv of
anhydrous CuCl2 in CH2Cl2. An insoluble light green
powder product was obtained. The elemental analysis
results for this green powder are, however, deviated
The Bi[p-C6H4(NMe2)]3Cl2 and Bi[p-C6H4CH2N(2-
Py)2]3Cl2 compounds react readily with silver salts, AgL,
where L is a carboxylate derivative, RCO2-, to form the
substituted complexes Bi[p-C6H4(NMe2)]3(O2CR)2 and
Bi[p-C6H4CH2N(2-Py)2]3(O2CR)2, respectively. Com-
pounds Bi[p-C6H4(NMe2)]3(O2CCF3)2 (5) and Bi[p-C6H4-
CH2N(2-Py)2]3(O2CCH3)2 (7) have been fully character-
ized by NMR, elemental, and X-ray diffraction analyses.
In the absence of silver salt and in the presence of
moisture and NaOH, the Bi[p-C6H4(NMe2)]3Cl2 com-
pound is converted to the dinuclear complex, Bi2[p-
C6H4(NMe2)]6Cl2(O) (6) in good yield. Compound 6 was
also commonly found as a trace product from the
reactions of compound 1 with silver salts.
(8) (a) Challenger, F. J . Chem. Soc. 1916, 109, 250. (b) Keck, J . M.;
Klar, G. Z. Naturforsch. (B) 1972, 27, 596.
(9) Hawley, D. M.; Ferguson, G. J . Chem. Soc. (A) 1968, 2539.
(10) Crystal data for Bi[p-C6H4(NMe2)]3Cl2/2 THF: hexagonal space
group R3c (# 161), a ) 12.521(3) Å, c ) 33.834(7) Å, V ) 4593(2) Å3, Z
) 6. The satisfactory refinement for this compound was not achieved
due to the disorder of the two THF molecules.
(6) Hawley, D. M.; Ferguson, G. J . Chem. Soc. A 1968, 2059.
(7) CAChe Scientific, Inc., USA, 1994.

Organobismuth(III) and Organobismuth(V) Complexes
Organometallics, Vol. 15, No. 26, 1996 5617
length of 2.32(1) Å is similar to that11 in BiPh3(O2-
CCF3)2. The noncoordinating O(2) and O(2′) atoms are
3.16 Å away from the Bi(1) center. The C-Bi-C angles
range from 110.9(7)° to 138(1)°, indicative of the sig-
nificant distortion from the ideal trigonal bipyramidal
geometry. There are two distinct environments for the
three aromatic ligands of 5 in the solid state, two of
which (C(1) and C(1′) rings) are perpendicular to the
Bi-O vector and are on the same side as the noncoor-
dinating O(2) and O(2′) atoms while the third one is
parallel to the Bi-O vector and is on the opposite side
from the O(2) and O(2′) atoms. However, in solution,
only one aromatic ligand environment is observed, as
established by 13C and H NMR spectroscopic analysis,
which can be attributed to the relatively low energy
required for the rotation of the Bi(1)-O(1) and Bi(1)-
O(1′) bonds.
1
F igu r e 1. ORTEP diagram showing the molecular struc-
ture of compound 1 with 50% thermal ellipsoids and
labeling scheme.
An ORTEP diagram showing the structure of the
dinuclear complex, Bi2[p-C6H4(NMe2)]6Cl2(O) (6), is
given in Figure 3. Important bond lengths and angles
are given in Table 2. Compound 6 contains two Bi[p-
C6H4(NMe2)]3Cl units linked together by an oxygen
atom. The Bi(1)-O(1) and Bi(2)-O(1) bond lengths,
2.12(3) and 2.02(3) Å, are comparable to those observed
in Bi2Ph6(ClO4)2(O), reported by Ferguson and co-
workers.12b The Bi(1)-O(1)-Bi(2) angle (166(1)°) devi-
ated from linearity by 14°, however, is much larger than
that (142.2(7)°) in Bi2Ph6(ClO4)2(O), possibly caused by
the increased steric bulkiness in 6. The geometry
surrounding each bismuth center is very close to the
ideal trigonal bipyramidal geometry, as evidenced by
the O-Bi-Cl angles (175.9(6)° and 179.5(8)°) and the
C-Bi-C angles ranging from 117(1)° to 123(1)°. The
Bi-Cl bond lengths (2.79(1) and 2.77(1) Å) are much
longer than those observed in Bi[p-C6H4(NMe2)]3Cl2 and
BiPh3Cl2, perhaps due to the stronger trans effect
induced by the oxo lingand than that by the chloro
ligand. Although several oxo-bridged dinuclear bis-
muth(V) complexes are known, few of them have been
characterized structurally. In fact, to our knowledge,
compound 6 is only the second example of a structurally
characterized oxo-bridged dinuclear bismuth complex.12
The ORTEP diagram showing the structure of com-
pound 7 is given in Figure 4. Selected bond lengths and
angles are listed in Table 2. The structure of 7 bears
some resemblance to that of compound 5, i.e., five-
coordinate with three carbon and two oxygen coordinat-
ing atoms. There are, however, several structural
features in 7 which are significantly different from those
in 5. First of all, the Bi(1)-O(1) and Bi(1)-O(3) bond
lengths, 2.19(2) and 2.25(2) Å, are considerably shorter
than those in 5. The noncoordinating O(2) and O(4)
atoms are at 2.80 and 2.81 Å, respectively, from the
bismuth center, much closer than those in 5, indicating
that some weak bonding interactions between the
bismuth and the noncoordinating oxygen atoms may
exist. Secondly, the geometry of the bismuth center in
7 is much more distorted from the trigonal planar
geometry than that in 5, as indicated by the C(22)-
Bi(1)-C(39) angle of 146(1)°, the C(5)-Bi(1)-C(22)
angle of 109(1)°, and the C(5)-Bi(1)-C(39) angle of
104(1)°. The geometry of compound 7 can therefore be
Sch em e 1
F igu r e 2. ORTEP diagram showing the molecular struc-
ture of compound 5 with 50% thermal ellipsoids and
labeling scheme.
An ORTEP diagram showing the molecular structure
of compound 5 is given in Figure 2. Important bond
lengths and angles are listed in Table 2. Compound 5
has an approximately trigonal bipyramidal geometry
with a crystallographically imposed C2 axis where the
Bi(1), N(2), C(9), and C(12) atoms lie. The Bi-C bond
lengths (2.00(6)-2.15(2) Å) are shorter than those
observed in compound 1, but comparable with those
observed in BiPh3(O2CCF3)2. The Bi(1)-O(1) bond
(11) Ferguson, G.; Kaitner, B. J . Organomet. Chem. 1991, 419, 283.
(12) (a) Goel, R. G.; Prasad, H. S. J . Organomet. Chem. 1972, 36,
323. (b) March, F. C.; Ferguson, G. J . Chem. Soc., Dalton Trans. 1975,
1291.

5618 Organometallics, Vol. 15, No. 26, 1996
Hassan et al.
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles (d eg)
Compound 1
atom
atom
distance
atom
atom
distance
atom
atom
distance
atom
atom
distance
Bi(1)
Bi(1)
N(1)
C(1)
C(15)
C(7)
2.25(1)
2.25(2)
1.42(2)
Bi(1)
N(1)
N(1)
C(9)
C(4)
C(8)
2.22(2)
1.41(2)
1.52(3)
N(2)
N(2)
N(3)
C(12)
C(24)
C(21)
1.36(2)
1.44(2)
1.42(3)
N(2)
N(3)
N(3)
C(23)
C(18)
C(22)
1.45(2)
1.41(3)
1.46(3)
atom
atom
atom
angle
atom
atom
atom
angle
atom
atom
atom
angle
atom
atom
atom
angle
C(1)
C(1)
C(9)
C(4)
C(7)
Bi(1) C(9)
Bi(1) C(15)
Bi(1) C(15)
95.6(5) Bi(1)
94.1(5) Bi(1)
93.7(6) Bi(1)
C(9)
C(9)
C(9)
N(1)
N(2)
N(2)
C(14) 122(1) C(18)
C(10) 121(1) C(21)
C(14) 122(1) Bi(1)
N(3)
N(3)
C(1)
C(1)
C(4)
C(4)
C(21) 115(2) C(18) N(3)
C(22) 120(2) Bi(1)
C(22) 122(2)
C(15) C(16) 120(1)
C(15) C(20) 123(1)
C(18) C(17) 124(2)
C(18) C(19) 119(2)
C(2)
C(6)
C(3)
C(5)
118(1) Bi(1)
122(1) N(3)
118(2) N(3)
121(2)
N(1)
N(1)
C(7)
C(8)
123(2)
118(2)
C(4)
C(12)
C(23)
C(8)
118(2) Bi(1)
C(23) 119(2) N(1)
C(24) 121(2) N(1)
C(12) N(2)
C(24) 119(2)
Compound 5
atom
atom
distance
atom
atom
distance
atom
atom
distance
atom
atom
distance
Bi(1)
Bi(1)
F(1)
F(3)
O(1)
C(1)
C(15)
C(15)
2.32(1)
2.15(2)
1.24(4)
1.30(4)
N(2)
Bi(1)
F(2)
O(1)
C(13)
C(9)
C(15)
C(14)
1.45(3)
2.00(6)
1.36(3)
1.16(3)
O(2)
N(1)
N(1)
N(2)
C(14)
C(7)
C(8)
1.24(3)
1.43(4)
1.43(4)
1.28(5)
N(1)
C(2)
C(14)
C(4)
C(3)
C(15)
1.31(3)
1.37(3)
1.63(4)
C(12)
atom atom atom
angle
atom atom
atom
angle
atom
atom
atom
angle
atom atom
atom
C(6)
angle
O(1)
O(1)
Bi(1) O(1′)
Bi(1) C(1)
176(1)
92.0(8) N(1)
89.6(8) O(1)
N(1)
C(4)
C(4)
Bi(1)
Bi(1)
C(3)
C(5)
C(9)
C(9)
123(3)
121(3)
87.8(5) C(12) N(2)
110.9(7) C(12) N(2)
C(4)
C(7)
N(1)
N(1)
C(8)
C(8)
C(13)
123(3) Bi(1) C(1)
113(3) O(1)
124(2) O(1)
120(2)
137(3)
C(14) O(2)
C(14) C(15) 115(3)
C(14) C(15) 107(3)
C(15) F(2)
C(15) F(3)
O(1′) Bi(1) C(1)
C(1)
Bi(1) C(9)
Bi(1) O(1)
Bi(1) C(1′)
138(1)
C(10) 127(2)
C(14) 109(2)
C(1)
C(13′) 124(2) O(2)
C(13′) 112(3) F(1)
C(2)
Bi(1) C(9)
C(10′) 127(2)
C(13) N(2)
Bi(1)
F(2)
105(3)
110(3)
N(2)
N(2)
C(12) C(11)
C(12) C(11)
122(2)
122(2)
C(1)
C(15) F(3)
120(2) F(1)
103(3)
C(4)
N(1)
C(7)
124(3)
Compound 6
atom
atom
distance
atom
atom
distance
atom
atom
distance
atom
atom
distance
Bi(1)
Bi(1)
Bi(1)
Bi(1)
Bi(1)
Bi(2)
Bi(2)
Bi(2)
Cl(1)
O(1)
C(1)
2.79(1)
2.12(3)
2.24(4)
2.14(4)
2.15(3)
2.77(1)
2.02(3)
2.24(4)
N(5)
N(6)
N(6)
N(6)
N(1)
N(1)
N(1)
N(2)
C(40)
C(44)
C(47)
C(48)
C(4)
C(7)
C(8)
C(12)
1.56(6)
1.41(5)
1.38(5)
1.48(5)
1.40(5)
1.40(5)
1.43(7)
1.41(4)
Bi(2)
Bi(2)
Cl(3)
Cl(4)
N(3)
N(4)
N(5)
C(33)
C(41)
C(49)
C(49)
C(24)
C(31)
C(36)
2.20(3)
2.24(4)
1.71(7)
1.79(8)
1.42(6)
1.38(5)
1.27(5)
N(2)
N(2)
N(3)
N(3)
N(4)
N(4)
N(5)
C(15)
C(16)
C(20)
C(23)
C(28)
C(32)
C(39)
1.46(5)
1.42(5)
1.41(4)
1.40(5)
1.37(5)
1.44(5)
1.45(5)
C(9)
C(17)
Cl(2)
O(1)
C(25)
atom atom
atom
angle
atom
atom
atom
angle
atom
atom
Bi(2)
atom
angle
atom
atom
atom
angle
Cl(1) Bi(1) O(1)
Cl(1) Bi(1) C(1)
Cl(1) Bi(1) C(9)
Cl(1) Bi(1) C(17)
175.9(6) C(15)
N(2)
N(3)
N(3)
N(3)
N(4)
N(4)
N(4)
N(5)
N(5)
N(5)
N(6)
N(6)
N(6)
C(1)
C(1)
C(1)
C(16) 121(4) O(1)
C(41)
90(1) N(1)
C(4)
C(4)
C(3)
C(5)
120(5)
117(5)
83(1)
87(1)
89(1)
93(1)
93(1)
94(1)
118(1)
C(20)
C(20)
C(23)
C(28)
C(28)
C(31)
C(36)
C(36)
C(39)
C(23) 124(4) C(25) Bi(2)
C(24) 117(4) C(25) Bi(2)
C(24) 119(4) C(33) Bi(2)
C(31) 117(4) Bi(1)
C(32) 126(4) C(4)
C(32) 117(4) C(7)
C(39) 123(4) C(12) N(2)
C(40) 124(4) C(12) N(2)
C(40) 113(4) N(2)
C(47) 124(4) N(2)
C(48) 120(4) Bi(1)
C(48) 115(4) Bi(1)
C(33) 120(1) N(1)
C(41) 120(1) N(4)
C(41) 120(1) N(4)
Bi(2)
C(8)
C(8)
C(28) C(27) 126(5)
C(28) C(29) 115(4)
N(1)
O(1)
O(1)
O(1)
C(1)
Bi(1) C(1)
Bi(1) C(9)
Bi(1) C(17)
Bi(1) C(9)
O(1)
N(1)
N(1)
167(1) C(4)
124(5) Bi(2) C(25) C(30) 117(3)
112(5) Bi(1) C(9)
C(7)
123(5)
C(10) 129(3)
C(14) 116(3)
C(15) 118(4) Bi(1) C(9)
C(16) 121(4) Bi(2) C(33) C(34) 121(3)
C(1)
C(9)
Bi(1) C(17) 124(1)
Bi(1) C(17) 117(1)
C(12) C(11) 122(4) Bi(2) C(33) C(38) 119(3)
C(12) C(13) 123(4) N(5)
C(17) C(18) 121(3) N(5)
C(17) C(22) 123(3) Bi(2) C(41) C(42) 119(3)
C(20) C(19) 123(4) Bi(2) C(41) C(46) 118(3)
C(20) C(21) 120(4) N(6)
C(25) C(26) 125(3) N(6)
Cl(2) Bi(2) O(1)
Cl(2) Bi(2) C(25)
Cl(2) Bi(2) C(33)
Cl(2) Bi(2) C(41)
179.5(8) C(44)
C(36) C(35) 122(5)
C(36) C(37) 120(5)
89(1)
83(1)
90(1)
91(1)
97(1)
C(44)
C(47)
Bi(1)
Bi(1)
C(2)
C(2)
C(6)
C(6)
123(3) N(3)
117(3) N(3)
120(4) Bi(2)
O(1)
O(1)
Bi(2) C(25)
Bi(2) C(33)
C(44) C(43) 116(4)
C(44) C(45) 119(5)
Compound 7
atom
atom
distance
atom
atom
distance
atom
atom
distance
atom
atom
distance
Bi(1)
Bi(1)
Bi(1)
Bi(1)
Bi(1)
O(1)
O(2)
O(3)
O(4)
O(1)
O(3)
C(5)
C(22)
C(39)
C(1)
C(1)
C(3)
C(3)
2.19(2)
2.25(2)
2.26(3)
2.19(3)
2.24(3)
1.26(3)
1.31(3)
1.32(3)
1.25(3)
N(5)
N(6)
N(6)
N(7)
N(7)
N(7)
N(8)
N(8)
N(9)
C(33)
C(34)
C(38)
C(45)
C(46)
C(51)
C(46)
C(50)
C(51)
1.39(5)
1.33(4)
1.44(4)
1.50(3)
1.39(3)
1.39(3)
1.31(4)
1.35(5)
1.34(3)
N(2)
C(1)
N(2)
N(1)
N(1)
N(1)
N(4)
C(8)
C(42)
C(12)
C(2)
1.29(4)
1.45(4)
1.46(5)
1.47(3)
1.44(4)
1.35(3)
1.43(3)
1.49(4)
1.54(4)
N(9)
C(3)
N(3)
N(3)
N(4)
N(4)
N(5)
C(25)
C(55)
C(4)
1.36(4)
1.48(4)
1.36(3)
1.28(4)
1.54(3)
1.41(4)
1.35(4)
1.60(4)
C(16)
C(11)
C(12)
C(17)
C(34)
C(11)
C(45)
C(17)
C(21)
C(28)
C(29)
C(29)
C(28)

Organobismuth(III) and Organobismuth(V) Complexes
Organometallics, Vol. 15, No. 26, 1996 5619
Ta ble 2. (Con tin u ed )
Compound 7
angle atom
atom
atom
atom
angle
170.6(8) C(29) N(4)
86(1) C(29) N(5)
88.7(9) C(34) N(6)
94.9(9) C(45) N(7)
atom
atom
atom
atom
atom
angle
atom
atom
atom
angle
O(1)
O(1)
O(1)
O(1)
O(3)
O(3)
O(3)
C(5)
C(5)
Bi(1) O(3)
Bi(1) C(5)
Bi(1) C(22)
Bi(1) C(39)
Bi(1) C(5)
Bi(1) C(22)
Bi(1) C(39)
C(34) 127(3) C(28) N(4)
C(33) 120(4) C(28) N(4)
C(29) 115(3) N(1)
C(34) 118(3) N(1)
C(11) C(8)
C(12) N(2)
C(29) C(30) 119(4)
C(33) C(32) 122(4)
115(3)
110(4)
C(38) 115(3) N(1)
C(46) 123(3) N(2)
C(51) 112(3) N(2)
C(51) 122(3) N(1)
C(50) 120(4) N(1)
C(55) 116(4) N(3)
C(12) C(13) 120(4) N(5)
C(12) C(13) 130(4) N(5)
C(16) C(15) 113(4) N(4)
C(17) N(3)
C(17) C(18) 122(4) N(6)
C(17) C(18) 119(3) N(6)
C(21) C(20) 127(4) Bi(1) C(39) C(40) 115(3)
C(22) C(23) 115(2) Bi(1) C(39) C(44) 122(3)
C(22) C(27) 124(3) N(7)
C(28) C(25) 113(3) N(7)
C(29) N(5)
C(29) C(30) 120(4) N(8)
C(50) C(49) 118(5) N(9)
85(1)
C(45) N(7)
C(34) N(6)
109(4)
91.8(6) C(46) N(7)
89.9(9) C(46) N(8)
118(3) N(4)
C(34) C(35) 125(4)
C(34) C(35) 126(4)
C(38) C(37) 119(4)
Bi(1) C(22) 109(1)
Bi(1) C(39) 105(1)
C(51) N(9)
O(1)
O(1)
O(2)
O(3)
O(4)
Bi(1)
C(1)
C(1)
C(1)
C(3)
C(3)
C(5)
O(2)
C(2)
C(2)
O(4)
C(4)
116(3) N(3)
131(3) Bi(1)
114(3) Bi(1)
122(3) N(4)
121(4) N(4)
C(22) Bi(1) C(39) 146(1)
Bi(1)
Bi(1)
O(3)
Bi(1)
C(11) N(1)
C(12) N(1)
C(17) N(3)
O(1)
O(3)
C(3)
C(5)
C(1)
C(3)
C(4)
C(6)
C(12) 118(3)
C(17) 120(3)
C(21) 120(3)
113(2)
105(2)
117(4)
118(3)
C(51) C(52) 122(4)
C(46) N(8) 117(4)
C(46) C(47) 121(4)
C(46) C(47) 122(4)
C(51) C(52) 116(3)
C(55) C(54) 129(5)
121(4) N(7)
C(10) 119(2) N(4)
C(17) 121(3) N(8)
C(16) 117(4) N(7)
C(11) N(1)
C(12) N(2)
N(7)
C(51) N(9)
121(4) N(9)
C(45) C(42) 113(3)
Compound 8
atom
atom
distance
atom
atom
distance
atom
atom
distance
atom
atom
distance
Bi
Bi
Bi
Bi
C(1)
C(9)
C(17)
C(25)
2.167(10)
2.194(8)
2.181(9)
2.192(8)
N(3)
N(3)
N(3)
N(4)
C(20)
C(23)
C(24)
C(28)
1.36(2)
1.43(1)
1.45(1)
1.37(1)
N(1)
N(1)
N(1)
N(2)
C(4)
C(7)
C(8)
C(12)
1.37(2)
1.46(1)
1.46(1)
1.37(1)
N(4)
N(4)
N(2)
N(2)
C(31)
C(32)
C(15)
C(16)
1.43(1)
1.43(1)
1.48(1)
1.45(1)
atom atom atom
angle
atom atom atom
angle
atom atom atom
angle
atom atom atom
C(7)
angle
C(1)
C(1)
C(1)
C(9)
C(9)
Bi
Bi
Bi
Bi
Bi
C(9)
C(17) 112.0(3) C(20) N(3) C(23) 120(1)
C(25) 107.7(3) C(20) N(3) C(24) 119.2(9) C(7)
C(17) 109.0(3) C(23) N(3) C(24) 117.7(9) C(12) N(2)
C(25) 110.0(3) C(28) N(4) C(31) 121.1(8) C(12) N(2)
106.1(3) C(15) N(2) C(16) 117.0(7) Bi
C(9)
N(1)
N(1)
C(14) 119.6(6) C(4) N(1)
C(8)
C(8)
120(1)
C(4)
122(1)
N(2) C(12) C(11) 122.1(9)
117.4(9) N(2) C(12) C(13) 121(1)
C(15) 119.5(8) N(3) C(20) C(21) 124(1)
C(16) 120.4(8) Bi
C(17) C(18) 119.7(7) Bi
C(25) C(26) 118.2(6)
C(25) C(30) 120.4(7)
C(17) Bi
C(25) 111.9(3) C(28) N(4) C(32) 119.3(9) Bi
119.7(7) C(31) N(4) C(32) 117.4(8) Bi
Bi
Bi
Bi
C(1) C(2)
C(1) C(6)
C(9) C(10) 119.0(7) N(1)
C(17) C(22) 120.0(6) N(3) C(20) C(19) 120(1)
C(28) C(27) 119(1) N(4) C(28) C(29) 124(1)
121.2(7) N(1)
C(4) C(3)
C(4) C(5)
123(1)
120(1)
N(4)
Compound 9
atom
atom
distance
atom
atom
distance
atom
atom
distance
atom
atom
distance
Bi(1)
Bi(1)
Bi(1)
Bi(1)
Ag(1)
C(1)
C(9)
C(17)
C(25)
Ag(1′)
2.15(2)
2.16(2)
2.18(3)
2.14(2)
3.211(5)
N(1)
N(1)
N(1)
N(2)
N(2)
C(4)
C(7)
C(8)
C(12)
C(15)
1.35(3)
1.43(3)
1.44(4)
1.38(3)
1.39(3)
Ag(1)
Ag(1)
Ag(1)
N(3)
Cl(1)
Cl(2)
Cl(2′)
C(24)
C(31)
2.367(8)
2.571(9)
2.540(8)
1.46(3)
N(2)
N(3)
N(3)
N(4)
N(4)
C(16)
C(20)
C(23)
C(28)
C(32)
1.46(3)
1.39(3)
1.48(3)
1.39(3)
1.44(3)
N(4)
1.41(4)
atom
atom
atom
angle
atom
atom
atom
C(6)
Bi(1) C(17) C(18) 118(2) C(4)
109.8(9) Bi(1) C(17) C(22) 123(2) C(7)
angle
atom
atom
atom
angle
atom
atom
atom
angle
C(1)
C(1)
C(1)
C(9)
C(9)
Bi(1)
Bi(1)
Bi(1)
Bi(1)
Bi(1)
C(9)
109.8(9) Bi(1) C(1)
106(1)
124(2) C(4)
N(1)
N(1)
N(1)
C(7)
C(8)
C(8)
122(3) N(3)
122(3) N(2)
116(3) N(2)
C(20) C(21) 123(2)
C(12) C(11) 119(3)
C(12) C(13) 122(3)
C(17)
C(25)
C(17)
C(25)
C(25)
107(1)
110.2(9) N(1)
113(1) N(1)
129.1(3) Bi(1) C(9)
130.9(4) Bi(1) C(9)
Bi(1) C(1)
C(2)
C(3)
C(5)
119(2) C(12) N(2)
123(3) C(15) N(2)
121(3) C(20) N(3)
C(15) 121(3) C(12) N(2)
C(16) 118(3) C(20) N(3)
C(24) 120(3) C(23) N(3)
C(31) 119(3) C(28) N(4)
C(16) 119(3)
C(23) 121(2)
C(24) 117(3)
C(32) 120(3)
C(4)
C(4)
C(17) Bi(1)
Cl(1)
Cl(1)
Cl(2)
Ag(1) Cl(2)
Ag(1) Cl(2′)
Ag(1) Cl(2′)
C(10) 123(2) C(28) N(4)
C(14) 123(2) C(31) N(4)
C(32) 120(3) N(3)
C(20) C(19) 119(3)
C(28) C(29) 120(3)
99.9(3) Bi(1) C(25) C(26) 120(2) N(4)
77.8(3) Bi(1) C(25) C(30) 126(2)
C(28) C(27) 123(3) N(4)
Ag(1) Cl(2)
Ag(1′)
described best as an intermediate between a trigonal
compound 7 retains the same structure in solution, one
would expect to observe three sets of chemical shifts due
to the three p-C6H4CH2N(2-Py)2 ligands. Indeed, the
proton NMR spectrum of compound 7 in the aromatic
region shows a complicated pattern which cannot be
assigned unambiguously. The 13C NMR spectrum of
compound 7, however, shows three well-resolved sets
of chemical shifts for each of the unique carbon atoms
on the phenyl ring and the carbon atom of the methyl-
ene group, where the three chemical shifts due to the
quaternary carbon atoms bonded to the bismuth center
differ most dramatically (see the Experimental Section).
The NMR results lead us to suggest that compound 7
bipyramid and a square pyramid. Thirdly, the environ-
ment surrounding each of the aromatic ligands, p-C6H4-
CH2N(2-Py)2, is not identical. The environments of two
of the aromatic ligands, C(22) and C(39), which are on
the same side as the noncoordinating O(2) and O(4)
atoms, are much closer than that of the third aromatic
ligand, C(5), which is on the opposite side of the O(2)
and O(4) atoms and occupies the axial position of the
distorted square pyramid. However, the pyridyl groups
of the C(39) ligand are oriented away from the pyridyls
of the C(5) ligand, while the pyridyls of the C(22) ligand
are oriented toward the pyridyls of the C(5) ligand. If

5620 Organometallics, Vol. 15, No. 26, 1996
Hassan et al.
F igu r e 5. ORTEP diagram showing the structure of
compound 8 with 50% thermal ellipsoids and labeling
scheme.
coordinating oxygen atoms are similar to those observed
in 7. Compound 7 is the first example of a tertiary
bismuth(V) complex containing the bidentate dipyridyl
functional group.
F igu r e 3. ORTEP diagram showing the molecular struc-
ture of compound 6 with 50% thermal ellipsoids and
labeling scheme.
Syn th eses a n d Str u ctu r es of Qu a ter n a r y Bis-
m u th (V) Com p lexes Bi[p-C6H4(NMe2)]4[P F 6] (8)
a n d {Bi[p-C6H4(NMe2)]4}2[Ag2Cl4] (9). It has been
observed earlier that when the compound BiPh3Cl2 is
reacted with silver salts where the anion is noncoordi-
-
nating, such as BF4 or PF6-, or weakly coordinating,
such as ClO4-, several products including the tetrahe-
dral cation [BiAr4]+ could be obtained.14 We performed
the reaction of Bi[p-C6H4(NMe2)]3Cl2 (4) with AgBF4 or
AgPF6 in a 1:2 ratio, which yielded mixed and unidenti-
fied products. In contrast, the reaction of Bi[p-C6H4-
(NMe2)]3Cl2 with TlPF6 in a 1:2 ratio in CH2Cl2 pro-
duced the new green crystalline compound Bi[p-C6H4-
(NMe2)]4[PF6] (8) in high yield. The mechanism for this
reaction has not been understood. Nevertheless, this
reaction provides a convenient way for the synthesis of
the quaternary bismuth(V) complex containing amino
groups. Compound 8 has been fully characterized by
NMR, elemental, and X-ray diffraction analyses. At 23
°C, the crystals of compound 8 have a light green color
and belong to the tetragonal space group P4/n. The
structure of 8 at 23 °C appeared to be tetrahedral but
displayed significant disorders. We therefore deter-
mined the structure of 8 by collecting the diffraction
data at -79 °C. At -79 °C, compound 8 changed color
to blue and the crystal unit cell changed to the mono-
clinic space group P21/n, apparently caused by a phase
transition.
F igu r e 4. ORTEP diagram showing the molecular struc-
ture of compound 7 with 50% thermal ellipsoids and
labeling scheme.
indeed retains its asymmetric structure in solution,
which is in sharp contrast to the behavior of compound
5. We believe that the structural rigidity of compound
7 could be caused by two factors, the possible weak
bonding interactions between Bi(1) and O(2) and O(4)
which would make the rotation of the Bi(1)-O(1) bond
and the Bi(1)-O(3) bond more energy demanding than
that in 5 and the steric bulkiness of the ligands in 7
which could also prevent the free rotation of the Bi(1)-
O(1) and Bi(1)-O(3) bonds by avoiding too many non-
bonding interactions. It is very likely that the second
factor plays a more important role than the first one
because the similar structural rigidity was not observed
in the analogous bismuth(V) complexes,13 Bi[p-C6H4-
(NMe2)]3(O2CR)2, where R is a non-trifluoromethyl
group and the distances between the Bi and the non-
The ORTEP diagram showing the structure of 8
determined by -79 °C is given in Figure 5. Important
bond lengths and angles are listed in Table 2. The
geometry of the cation, Bi[p-C6H4(NMe2)]4+, is tetrahe-
dral, as indicated by the C-Bi-C angles ranging from
106.1(3)° to 112.0(3)°. The Bi-C bond lengths,
2.167(10)-2.194(8) Å, are comparable with those ob-
served in the analogous compound BiPh4[ClO4] reported
(13) Hassan, A.; Wang, S. Organometallics, submitted for publica-
tion.
(14) (a) Doak, G. O.; Long, G. G.; Kakar, S. K.; Freedman, L. D. J .
Am. Chem. Soc. 1966, 88, 2342. (b) Beaumont, R. E.; Goel, R. G. J .
Chem. Soc., Dalton Trans 1973, 1394. (c) Bordner, J .; Freedman, L.
D. Phosphorus 1973, 3, 33.

Organobismuth(III) and Organobismuth(V) Complexes
Organometallics, Vol. 15, No. 26, 1996 5621
the anion are bridged by two chlorine atoms with the
Ag(1)-Ag(1′) separation distance being 3.211(5) Å. The
geometry of the silver atom is approximately trigonal
planar. The terminal Cl(1)-Ag(1) bond length, 2.367(8)
Å, is significantly shorter than the bridging Cl(2)-Ag(1)
and Cl(2′)-Ag(1) bond lengths, 2.571(9) and 2.540(8) Å.
Examples of three-coordinate dinuclear silver(I) com-
plexes are not uncommon.15a Silver halide complexes
have been known to have the tendency to aggregate via
the halide bridge forming typically four-coordinate
oligomers.15 To our knowledge, the three-coordinate
2-
dinuclear anion Ag2Cl4 is previously unknown, per-
haps due to its poor stability. Although the formation
mechanism of 9 has not been established, we believe
that the unusual Ag2Cl4 anion in compound 9 was
F igu r e 6. Unit cell packing diagram showing the cation
and anion channels of compound 8 down the b axis.
2-
trapped and stabilized by the bulky cation Bi[p-C6H4-
+
(NMe2)]4
.
Con clu sion
An improved synthesis and a full characterization for
the compound Bi[p-C6H4(NMe2)]3 (1) have been achieved.
New tertiary bismuth(III) complexes containing func-
tional groups, Bi[p-C6H4(CH2NPri )]3 (2) and Bi{p-C6H4-
2
F igu r e 7. ORTEP diagram showing the structure and the
relative location of the cation and anion in compound 9 with
50% thermal ellipsoids and labeling scheme.
[CH2N(2-Py)2]}3 (3), have been synthesized and char-
acterized. The bismuth(V) derivatives of compounds 1
and 3 can be obtained via oxidation and substitution
reactions. The structure and composition of the prod-
ucts obtained from the reaction of BiAr3Cl2 with AgL
are highly dependent on the nature of the anion L and
the reaction conditions as demonstrated by the reactions
of Bi[p-C6H4(NMe2)]3Cl2 with silver salts. The BiAr3-
(O2CR)2 compound can be best described as a distorted
trigonal bipyamid. The compound TlPF6 is a better
reagent than AgPF6 or AgBF4 for the synthesis of
quaternary bismuth(V) complexes. The interactions
between the noncoordinate oxygen atoms and the
bismuth center are very weak and negligible as dem-
onstrated by the high fluxionality of the Bi[p-C6H4-
(NMe2)]3(O2CR)2 compounds in solution. The quater-
nary bismuth(V) complex, Bi[p-C6H4(NMe2)]4[PF6] (8),
displays an unusual dynamic behavior in solution. The
nature and the mechanism of this dynamic process have
yet to be established.
by Bordner and Freedman14c and BiPh4[tosylate] and
BiVPh4[BiIIIPh2(O2CCF3)2] reported by Barton and co-
workers.1d However, weak Bi-O bonding interactions
appeared to be present in Barton’s compounds. In the
crystal lattice, the Bi[p-C6H4(NMe2)]4+ cations are stacked
along one dimension to form a cationic channel. Simi-
-
larly, the PF6 anions are also stacked to form an
anionic channel as shown by the unit cell packing
diagram (Figure 6). Bismuth(V) complexes containing
the p-C6H4(NMe2) ligand are usually colorless or light
yellow. The unusual green color of compound 8 is
believed to be caused by ligand to metal charge transfer,
possibly involving the lone pair of the nitrogen atom
since the analogous compound, BiPh4(ClO4), is colorless.
In solution, compound 8 appears to undergo some
1
dynamic processes as evident by the broad H and 13C
NMR signals of the phenyl group at 293 K. When the
solution was cooled to 180 K, relatively sharp and
resolved signals were observed. Dynamic processes
involving a tetrahedral geometry and a closed d10
electronic configuration on the metal center are rare.
Further investigation on the electronic structure and
the dynamic behavior of compound 8 is in progress.
Compound 8 is closely related to compound 9, {Bi[p-
C6H4(NMe2)]4}2[Ag2Cl4], obtained as a trace product
from the reactions of Bi[p-C6H4(NMe2)]3Cl2 with a
variety of silver salts, Ag(O2CR). Attempts to synthe-
size compound 9 by reacting Bi[p-C6H4(NMe2)]3Cl2 with
AgCl have not been successful. The structure of 9 was
determined by X-ray diffraction analysis. An ORTEP
diagram showing the structure and the relative location
of the cation and the anion is given in Figure 7. Selected
bond lengths and angles are listed in Table 2. The
structure of the cation, Bi[p-C6H4(NMe2)]4+, is very
similar to that in compound 8. The most interesting
Ack n ow led gm en t. We thank the Natural Science
and Engineering Research Council of Canada for finan-
cial support of this work and J im Britten for the X-ray
data collection of compound 8.
Su p p or tin g In for m a tion Ava ila ble: Tables of crystal-
lographic data, atomic coordinates, thermal parameters, and
bond lengths and angles (56 pages). Ordering information is
given on any current masthead page.
OM960641W
(15) (a) Comprehensive Coordination Chemistry; Wilkinson, G.,
Gillard, R. D., McCleverty, J . A., Eds.; Pergamon Press: Oxford, 1987;
Vol. 5, Chapter 54. (b) Stomberg, R. Acta Chem. Scand. 1969, 23, 3498.
(c) Thackeray, M. M.; Coetzer, J . Acta Crystallogr. Sect. B 1975, 31,
2339. (d) Brown, I. D.; Howard-Lock, H. E.; Natarajan, M. Can. J .
Chem. 1977, 55, 1511.
2-
feature of compound 9 is the Ag2Cl4 anion which is
situated between the cations. The two silver atoms in