TehahedronL*ca.Vol.33.N0.~.

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66534656.1992 OC'4C'4039192
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PrintcdinOreatBriti PaguMnpressL*d

Synthesis* Structure, and Reactions of

lo-Bi-4 Organobismuth Ate Complexes

Xiang Chew, Yohsuke Yamamoto, Kin-ya Akiba,*

Satoshi Yoshida#, Masanori Yasui#, and Fujiko Iwasaki#*

Departmentof Chemistry,Faculv of Science, HiroshimaUniversity,

I -3-I ‘Kagamiyama.Higashi-Hiroshima724! Japan,
#Departmentof AppliedPhysiizsand Chemistry,
The Universityof Electra-Communications,Chofi-shi, Tokyo182, Japan

Summary: The anionic lo-Bi-4 species @a, 2b) were synthesized by the reaction of BiCl3 with 2 equiv of
lithium 2-(2-lithiophenyl)-2-propoxide derivatives (la, lb). The X-ray crystallographic analysis showed 2a-
E@N+ to be distorted pseudotrigonal bipyramid in geometry. Reaction .of dimethyl-substituted 2b-Li+ with
methyl iodide took place exclusively not at the bismuth but at the oxygen to give an ether 4.

In recent years, there has been a growth of interest in organobismuth compounds.1 However, because
of the low stability of hypervalent organobismuth compounds only very few examples T rem fm
tetracoordinate organobiimuth ate complexes. 2 Some bismuth compkxes such as Ph2Bi-X2 E@J+
(X=Cl,Br,I), PhnBi-X4-n PhqAs+(n=l,2;X=Cl,Br, SCN) we- jsolated in 1969.a Barto& et al. repotted
the structureof [Ph2Bi(OCtZXI@)2]- PhqBi+, whiqh has been the only one species whose structure (distorted
trigonal bipymmid) was determined by X-ray crystilographic analysisT2b but chemical characteristics were
not provided for the bismuth complex.
During our nzcent investigation on hy&rvalint organobismuth chemistry pentacoordinate and even
hexacoordinate (lO-Bi-5 and 12-Bi-6) compounds could be characterized by use of a bidentate ligand (la).3
We report here the preparation of novel tetracoordmate organobismuth ate complexes (lO-Bi-4: 2a, 2b) by
use of la and lb, molecular structure of 2a-EtqN+, and some reactions of 2 with ekctrophiles.
Synthesis of symmetrically substituted lO-Bi-4 complexes (2a. 2b) from BiC13 and dilithio derivatives
(la. lb) of substituted cumyl alcohols is outlined in Scheme 1. As a typical example, the dilithiated nagent
(la),4 which was prepared from bis(trifluoromethyl)benzyl alcohol (1 mL, 5.98 mmol), n-BuLi (12.4 mmol
in 8.0 mL of hexane), and NJVJV’,ZV’-tetramethylethylenediamineWA: 0.2 mL, 2.42 mmol) and a
small amount (ca. 1.5 mL) of THP. was added dropwise to a cold (-78 “C) stirredsolution ofBiC13 (0.94 g,
2.98 mmol) in 15 mL of THF. The mixture was stirred for 5 h at -78 “C and quenched with water. Almost
pure 2a-Li+ was obtained in 64% yield after recrystallization from acetone-ether. Compound 2a-Li+ was
unstable to chmmatographic treatment (Sio;l) or acids and gave protonated bismuth compound 3a.5 which
returned to 2a-K+ after treatment with K2cO3. Therefore, 2a-Li+ or 2a-K+ was treated with E@FBr to
give 2a-EtqN+, which was stable toward atmospheric moisture and gave correct elemental analysis.6
Reaction of BiC13 with the 2 equiv of lb at -78 “C!for 5 h gave 2b-Li+ . Compound 2b-EtqN+ could
be prepared by a similar method as Za-EtqN+. but in contrast 2b-EtqN+ was unstable to atmospheric
6654

moisture and gave protonated bismuth compound 3b7 in 66% yield during~mcrystallization from benrene-
methanol.

Scheme 1.

RR
Et,,N+Bif
OLi
2eq.
2a-&N+: R=-CFs
2b-E&,N+: R=-CH3
BiC13 ______t
la: R=-CF,
1 b: R=-CH3

2a-Li+: R=-Cs
2b-Li+: R=-CH3
3a: R=-CF3
3b: R=-CH3

The structure of 2a-EtqN+ has been

elucidated by X-ray crystallography.* The
ORTEP drawing is shown in Figure 1. The
geomeny about the bismuth atom is distorted
pseudotrigonal bipyramid, where the carbon
atoms adjacent to bismuth occupy the equatorial
plane with a C-Bi-C angle of 94.1“. The apical
positions of the trigonal bipyramid are occupied
by the two oxygen atoms with the O-Bi-0 angle
of 159.7O. The lone pair of electrons is
considered to occupy one equatorial position. The
apical Bi-0 bond lengths are 2.273 A and 2.306
A,which ate longer than the sum of the bismuth
and oxygen covalent radii (2.18A),9thus these
Bi-0 bonds are confirmed to form a hypervalent
Figure 1
3-center 4-electron bond. In the crystals, there are
ORTEP Drawing of 2a-EtqN+
no special interactions between cations and anions
except van der Waals interaction.
The lone pair electrons of 2a-EtqN+ were poorly reactive toward electrophilic reagents, thus 2a-Et@
did not react with Me1 in refluxing TI-IF for 12 h. But 2b-Li+ did react with Me1 at the oxygen atom to give
O-methylated products 4,lo which gave correct elemental analysis (Scheme 2). These results were sharply
 6655

different from that of the corresponding lO-Sb-4 antimony complex, which reacted with Me1 at the central
antimony atom to give a pentacoonlinate compoundll
The reaction with sulfuryl chloride took place with the lone pair electrons of 2a-K+ in CH2Cl2 to afford
lO-Bi-5 chlorobismuthorane 5l2 almost quantitatively at room temperature. The pentaanndinate compound 5
was sensitive to atmospheric moisture but could be recrystallized from ether to form colorless crystals and
gave correct elemental analyses.

Scheme 2

SO,Cl,

M+= K+

2a MeI THF reflux

w
M+=.li+( orEt4N+)

Me1

THF r.t.
4
2 b-Li’ H,C- ‘CH,

We could not observe any evidence for a ring-opening equilibrium shown in eq 1. Thus, 1% NMR of
2a-EtqN+ and 2a-Li+ in acetone-de showed only one pair of quartets (ca. 6 -74.5 and -77.4) between +50
“C and -50 “C. The fact that 19F NMR of 613 showed two pairs of quartets at rather different field (8 -67.1.
-67.6 and -72.5, -76.2) strongly supports that the tetracoordinate complex 2a exists as a bicyclic compound
in solution. This should be the case for 2b. Although we cannot rule out completely the possibility of the
presence of very fast ring-opening equilibrium with these facts, we believe at present that protonation and
methylation of 2 take place at the oxygen atom in the five-membered ring directly and chlorination does at the
bismuth atom.

RR RR

(4 1)

2 a-M+:R=CF3 2a’-M+:R=CF3 6
2 bM+:R=CH3 2 b’-M+:R=CH3
References

1) (a) Finet, J.-P. Chem. Rev. 1989.89, 1487; (b) Freedman L. D.; Doak, G. 0. C/rem. Rev. 1982.82,
15;. (c) Barton, D. H. R.; Ozbalik, N.; Ramesh, M. Tetrahedron 1988,44,5661; (d) Ogawa, T.;
Murafuji, T.; Suzuki, H. J. Chem. Sot. ‘Chem. Commun. 1989, 1749.
2) (a) Faraglia. G. J. Organomet. Chem. 1969,20,99; (b) Barton, D. H. R.; Charpjot, B.; Dau, E. T. H.;
Motherwell. W. B.;, Pascard. C.; Pichen, C. Helv. Chim. Acta 1984,67, 586.
3) Akiba. K.-y.; Ohdoi, K.; Yamamoto, Y. Tetrahedron Lert. 1988,29, 3817; Akiba, K.-y.; Ohdoi. K.;
Yamamoto, Y. Tetrahedron Len. 1989,30,953.
4) Perozzi. E. F.; Michalak, R. S.; Figuly, G. D.; Stevenson, W. H. III; Dess, D. B.; Ross, M. R.; Martin,
J. C. J. Org. Chem. 1981,46, 1049.
5) 3a: 1H NMR (acetone-d6) 8 7.29 (td, J = 5.8. 1.4 Hz, 2H), 7.50 (td. J = 5.8, 1.4 Hz, W), 7.61-7.68
(m, 2H). 8.25 (dd. J = 5.8. 1.4 Hz, 2H); 19F NMR(acetoned6) 6 -76.3 (brs, 12F); m.p. 100-102 OC
(dec).
6) 2a-Et4N+: JH NMR (acetone-dg) 8 1.38 (tt, J = 7.3, 1.9 Hz, 12H), 3.47 (q, J = 7.3 Hz, 8H), 7.22-7.70
(m, 6H), 8.23-8.33 (m, 2H); 19F NMR (acetone-d6) 6 -74.5 (q, J = 8.8 Hz, 6F), -77.4 (q. J = 8.8 Hz,
6F); Anal. Calcd for C26H28F12NG2Bi: C, 37.92; H, 3.43; N, 1.70; Found: C, 38.10; H, 3.36; N,
1.46; m.p. 167-168 “C.
7) 3b: 1H NMR (CDCl3) 6 1.75 (brs, 12H), 7.1 l-7.50 (m, 6H), 8.08 (d, J = 7.3 Hz, 2H); Anal. Calcd for
ClgH2JCQBi: C. 45.20; H, 4.43; Found: C. 45.13 ; H, 4.88; m.p. 227-228 “C.
8) Crystal data for 2a-EtqN+: space group P2l/n, a=15.547 (2) A, b=lSOO(2)A, c=l1.996 (2) A.
@=+X).19
(2)‘. 2%. 4665 reflections used, R=O.045. The atomic coordinates have been deposited with
the Cambridge Crystallographic Data Cenue.
9) Dean, J. A. Lange’s Ha&book of Chemistry, 11th Ed; McGraw-Hill: New York, 1973; ~3-119.
10) 4: 1H NMR (CDC13) 6 1.58 (brs, 12H), 3.74 (s, 3H), 7.10-7.70 (m, 7H), 8.20-8.40 (m, 1H); Anal.
Calcd for ClgH2302Bi: C, 46.35; H, 4.71; Found: C, 46.72 ; H, 4.74; m.p. 200-202 “C.
11) Akiba, K.-y.; Nakata, H.; Yamamoto, Y.; Kojima, S. unpublished results
12) 5: 1H NMR (CDC13) 6 7.70-8.15 (m, 6H), 8.85-8.96 (m, 2H); J9F NMR (CDC13) 6 -74.00 (s, 12F);
Anal. Calcd for CJgHgFJ202ClBi: C, 29.67; H, 1.11; Found: C, 29.89; H, 0.92; m.p. 225-227 OC!
ew.
13) Synthesis of 6 will be published later. 6: lH NMR (CDC13) 6 4.38 (brs, 3H), 7.25-7.96 (m, 7H), 8.34
(d, J = 7.6 Hz, 1H); 19F NMR (CDC13) 6 -67.1 (bq, 3F), -67.6 (bq, 3F), -72.5 (q. J = 8.6 Hz, 3F).
-76.2 (q, J = 8.6 Hz, 3F); Anal. Calcd for Cl9Hl lFl202Bi: C, 32.22; H, 1.56; Found: C, 32.44, H,
1.33; m.p. 220-222 “C (dec).
14) Acknowledgement: Partial support of this work was provided by the Ministry of Education, Science. and
Culture of the Japanese Government (Nos. 02247 103.03233104) and is heartily acknowledged.

(Received in Japan 18 March 1992; accepted 20 May 1992)