Hybrid dibismuthines and distibines: Preparation and properties of antimony and bismuth oxygen, sulfur, and nitrogen donor ligands

Article abstract of DOI:10.1021/om1010148

The hybrid dibismuthines O{(CH₂)₂BiPh ₂}₂, MeN(CH₂-2-C₆H ₄BiR₂)₂, and S(CH₂-2-C ₆H₄BiR₂)₂ (R = Me, Ph

Full text of DOI:10.1021/om1010148

Organometallics 2011, 30, 895–904 895
DOI: 10.1021/om1010148
Hybrid Dibismuthines and Distibines: Preparation and Properties of
Antimony and Bismuth Oxygen, Sulfur, and Nitrogen Donor Ligands
Sophie L. Benjamin, Louise Karagiannidis, William Levason,* Gillian Reid, and
Michael C. Rogers
School of Chemistry, University of Southampton, Southampton, U.K. SO17 1BJ
Received October 26, 2010
The hybrid dibismuthines O{(CH2)2BiPh2}2, MeN(CH2-2-C6H4BiR2)2, and S(CH2-2-C6H4BiR2)2
1
(R = Me, Ph), have been prepared and characterized by microanalysis, H and 13C{1H} NMR
spectroscopy, and FAB mass spectrometry. The X-ray structures of O{(CH2)2BiPh2}2 and S(CH2-2-
C6H4BiPh2)2 show close to symmetrical hypervalent interactions between the O or S atoms and both
bismuth centers. The antimony analogue S(CH2-2-C6H4SbMe2)2 is quaternized by MeI to [S(CH2-2-
C6H4SbMe3)2]I2, which also shows a hypervalent S Sb interaction, but in this case to only a single
3 3 3
þ
antimony center. Complexes of these and related ligands with the CpFe(CO)2 group, of the type
[{CpFe(CO)2}2L][BF4]2 (L = O{(CH2)2BiPh2}2, MeN(CH2-2-C6H4BiR2)2, S(CH2-2-C6H4BiR2)2, O-
{(CH2)2SbR2}2, S(CH2-2-C6H4SbMe2)2, MeN(CH2-2-C6H4SbMe2)2, Ph2Sb(CH2)3SbPh2), have been
prepared and characterized by microanalysis (antimony complexes only), 1H and 13C{1H} NMR and IR
spectroscopy, and ESþ mass spectrometry. The X-ray crystal structure of [{CpFe(CO)2}2-
{O{(CH2)2SbMe2}2}][BF4]2 shows a hypervalent Sb O contact to one of the antimony centers,
3 3 3
whereas no hypervalent contacts are seen in the structure of [{CpFe(CO)2}2{MeN(CH2-2-
C6H4SbMe2)2}][BF4]2. IR (carbonyl region) and NMR spectroscopy indicate that, uniquely,
[{CpFe(CO)2}2{MeN(CH2-2-C6H4BiPh2)2}][BF4]2 shows hypervalent N Bi interactions in both
3 3 3
the solid and solution, but for the other dibismuthine complexes, there is evidence for inequivalence
of the iron centers (and hence hypervalency) only in the solid state. Spectroscopic data indicate
that hypervalent interactions are absent in [{CpFe(CO)2}2{MeN(CH2-2-C6H4SbMe2)2}][BF4]2 and
[{CpFe(CO)2}2{S(CH2-2-C6H4SbMe2)2}][BF4]2, but present in solid [{CpFe(CO)2}2{O{(CH2)2-
SbR2}2}][BF4]2. The preparation and X-ray structure of [CpFe(CO)2{BiPh2(o-C6H4OMe)}][BF4] is
also reported, but attempts to isolate [CpFe(CO)2(BiPhMe2)]][BF4] resulted in rapid scrambling of the
substituents at bismuth to give [CpFe(CO)2(BiPh3-nMen)][BF4] (n = 0-3).
Introduction
complexes cannot be obtained directly.3 It is also clear that the
organometallic chemistry supported by tertiary stibines is
significantly different from that of the lighter analogues.2
Although there is an extensive organic chemistry of bismuth,4
bismuthine ligands have been very little studied, partially due
to their poor σ-donor power and to the reactive C-Bi bonds
which are prone to fission in the presence of some metals.2 The
majority of bismuthine complexes are with metal carbonyls
and contain only symmetrical monodentate BiR3 ligands;2,5
only one dibismuthine, p-Ph2BiC6H4BiPh2, has been com-
plexed (with Cr and W carbonyls),6 and there are a few hybrid
ligands containing bismuth in combination with O, N, P, etc.
The synthesis, coordination and organometallic chemistry
of phosphine and, to a rather lesser extent, arsine ligands
have been major research areas for the last 70 years. Detailed
studies of the heavier analogues, stibines, have only been
carried out in the last 25 years or so, the neglect partially
reflecting the more difficult syntheses of the ligands but mostly
due to the view that they were “similar but poorer” ligands in
comparison to phosphines.1,2 This viewpoint is no longer
tenable, and tertiary stibines have a chemistry significantly
different from that of their lighter analogues, most clearly
demonstrated by the seminal work of Werner,3 who prepared
the first examples of bridging ER3 (E = P, As, Sb) ligands with
SbiPr3 and who showed that metathesis with PR3 or AsR3 led
to examples of these as bridging ligands, although the latter
(4) (a) Gmelin Handbuch der Anorganische Chemie, 8th ed.; Springer-
Verlag: New York, 1978; Bismuth-organic Compounds. (b) Akiba, K. Y.;
Yamamoto, Y. In Chemistry of Organic Arsenic, Antimony, and Bismuth
Compounds; Patai, S., Ed.; Wiley: New York, 1994; p 761. (c) Suzuki, H.;
Matano, Y. In The Chemistry of Arsenic, Antimony and Bismuth; Norman,
N. C., Ed.; Blackie: London, 1998; p 207.
(1) (a) Levason, W.; McAuliffe, C. A. Acc. Chem. Res. 1978, 11, 363.
(b) Champness, N. R.; Levason, W. Coord. Chem. Rev. 1994, 133, 115.
(2) (a) Levason, W.; Reid, G. In Comprehensive Coordination Chem-
istry II; McCleverty, J. A., Meyer, T. J., Eds.; Elsevier: 2004, Vol. 1, p 377.
(b) Levason, W.; Reid, G. Coord. Chem. Rev. 2006, 250, 2565.
(3) Werner, H. Angew. Chem., Int. Ed. 2004, 43, 938.
(5) (a) Schumann, H.; Eguren, L. J. Organomet. Chem. 1991, 403, 183.
(b) Holmes, N. J.; Levason, W.; Webster, M. J. Organomet. Chem. 1997,
545- 546, 111. (c) Breunig, H. J.; Lork, E.; Rat, C. I.; Wagner, R. P.
J. Organomet. Chem. 2007, 692, 3430. (d) Breunig, H. J.; Borrmann, T.;
Lork, E.; Moldovan, O.; Rat, C. I.; Wagner, R. P. J. Organomet. Chem. 2009,
694, 427.
r
2011 American Chemical Society
Published on Web 01/24/2011
pubs.acs.org/Organometallics

896 Organometallics, Vol. 30, No. 4, 2011
Benjamin et al.
Scheme 1. Hybrid Dibismuthine Ligands
donor atoms,1,7 although characterization of complexes of the
last group has been poor by current standards. Here we report
the synthesis of several new ligands containing two bismuthine
groups in combination with a single O, N, or S donor atom and
some antimony analogues and illustrate their chemistry by
complexation to the [(η5-Cp)Fe(CO)2]þ acceptor unit. There is
a great deal of current interest in hypervalent interactions
N(O) Bi(Sb) in organo-antimony and -bismuth compounds
3 3 3
and their complexes,8-10 and there is the possibility of using
metal complexes of the bismuth ligands as precursors for
bismuth-metal alloys or nanoparticles by thermal deposition
techniques.
Results and Discussion
Polydentate Bismuth Ligands. The relative fragility of the
Bi-C linkage, which is prone to both fission and scrambling of
substituents on the bismuth center, necessitates the introduc-
tion of the bismuth groups in the final stage of the ligand
syntheses and under carefully controlled (mild) conditions. We
found that careful control of the reaction temperature, reagent
stoichiometry, and reaction times were all key to obtaining
pure samples of the bismuth ligands; relatively minor changes
can result in very impure products and low yields. In the
introduction of Ph2Bi- groups, Ph2BiBr (made by compro-
portionation of BiBr3 and Ph3Bi in a 1:2 ratio in diethyl ether
solution) is the key reagent; Ph2BiCl is poorly soluble, espe-
cially at low temperatures, and this causes insuperable pro-
blems in maintaining control of the reaction stoichiometry.
Similarly, we used Me2BiBr as the preferred source of Me2Bi-
groups; it is not necessary to isolate Me2BiBr, which was made
in situ in thf from BiBr3 and MeLi (1:2) at -78 °C and used
immediately. With the R2BiBr reagents in hand, the two routes
to hybrid polybismuthine ligands are either direct reaction
with the appropriate lithio derivative or reaction with Na/
liquid NH3 to form NaBiR211 and subsequent reaction with an
organohalide (Scheme 1); where both routes appear feasible,
the former is far preferable and gives higher yields.
O{(CH2)2BiPh2}2 (3) was obtained in good yield (55%)
by reaction of I(CH2)2O(CH2)2I with NaBiPh2 in liquid
ammonia. Use of X(CH2)2O(CH2)2X (X = Cl, Br) results in
incomplete substitution of the halide, indicative of poor
nucleophilicity of the bismuthide ion. 3 is a white air-stable
solid, but is air-sensitive in solution, readily identified by its 1H
and 13C{1H} NMR spectra (Experimental Section), although
in contrast to most of the other ligands in this work, it showed
only Ph2Biþ and PhBiþ as significant ions in the FAB mass
spectrum. In contrast to corresponding P, As, and Sb ligands,
neither quaternization with RX nor halogenation (to Bi(V)
species) is possible.4b,c The structure of 3 (Figure 1) shows a
pyramidal arrangement of organic groups about bismuth, with
C-Bi-C angles less than 96°, consistent with the Bi-C bonds
having high Bi 6p character,2b,6 and the angle at the oxygen
bridge C(15)-O(1)-C(14) is 112.1(4)°. The conformation
shows close to symmetric hypervalent interactions between
(6) Holmes, N. J.; Levason, W.; Webster, M. J. Organomet. Chem.
1999, 584, 179.
(7) (a) Levason, W.; McAuliffe, C. A.; Sedgwick, R. D. J. Organomet.
Chem. 1976, 122, 531. (b) Levason, W.; Sheihk, B.; McCullough, F. P.
J. Coord. Chem. 1982, 12, 53. (c) Levason, W.; McAuliffe, C. A.; Murray,
S. G. J. Chem. Soc., Dalton Trans. 1977, 711.
the oxygen and both bismuth atoms, Bi(1) O(1) = 3.203(3)
3 3 3
˚
and Bi(2) O(1) = 3.126(3) A, which are within the sum of
3 3 3
12
the van der Waals radii (3.52 A). Although hypervalent
(8) (a) Soran, A.; Breunig, H. J.; Lippolis, V.; Arca, M.; Silvestru, C.
Dalton Trans. 2009, 77. (b) Balazs, L.; Breunig, H. J.; Lork, E.; Silvestru, C.
Eur. J. Inorg. Chem. 2003, 1361. (c) Balazs, L.; Stanga, O.; Breunig, H. J.;
Silvestru, C. Dalton Trans. 2003, 2237. (d) Breunig, H. J.; Koenigsmann, L.;
Lork, E.; Philipp, N.; Nema, M.; Silvestru, C.; Soran, A.; Varga, R. A.;
Wagner, R. Dalton Trans. 2008, 1831. (e) Breunig, H. J.; Ghesner, I.;
Ghesner, M. E.; Lork, E. Inorg. Chem. 2003, 42, 1751. (f) Balazs, L.;
Breunig, H. J.; Lork, E.; Soran, A.; Silvestru, C. Inorg. Chem. 2006, 45,
2341. (g) Soran, A.; Silvestru, C.; Breunig, H. J.; Balazs, L.; Green, J. C.
Organometallics 2007, 26, 1196. (h) Okajima, S.; Yasuike, S.; Kakusawa,
N.; Osada, A.; Yamaguchi, K.; Seki, H.; Kurita, J. J. Organomet. Chem.
2002, 656, 234. (i) Yasuike, S.; Kishi, Y.; Kawara, S.; Yamaguchi, K.; Kurita,
J. J. Organomet. Chem. 2006, 691, 2213. (j) Opris, L. M.; Preda, A. M.;
Varga, R. A.; Breunig, H. J.; Silvestru, C. Eur. J. Inorg. Chem. 2009, 1187.
(k) Opris, L. M.; Silvestru, C.; Breunig, H. J.; Lork, E. Dalton Trans. 2003,
4367. (l) Kakusawa, N.; Tobiyasu, Y.; Yasuike, S.; Yamaguchi, K.; Seki, H.;
Kurita, J. J. Organomet. Chem. 2006, 691, 2953. (m) Zhang, X.-W.; Xia, J.;
Yan, H.-W.; L., S.-L.; Yin, S.-F.; Au., C.-T.; Wong, W.-Y. J. Organomet.
Chem. 2009, 694, 3019. (n) Breu, E.; Falke, R.; Elner, A.; Beuter, M.; Kolb,
U.; Drager, M. Polyhedron 1994, 13, 365. (o) Drager, M.; Schmidt, B. M.
J. Organomet. Chem. 1985, 290, 133.
˚
interactions between bismuth and heteroatoms such as O, N,
and S are well established,8 these usually involve a single
bismuth center and are, as might be expected, markedly shorter
than the present example.
Repeated attempts to isolate O{(CH2)2BiMe2}2 from the
reaction of NaBiMe2 with I(CH2)2O(CH2)2I were unsuccess-
ful, the reaction generating large amounts of elemental Bi and a
complex mixture of organic fragments. Although O{(CH2)2-
SbMe2}2 is known and is stable in the absence of air, O{-
(CH2)2AsMe2}2 is unstable and cleaves readily at the C-O
link on heating or reaction with metal salts to yield 2-
(dimethylarsino)ethanol.10
8l
Dilithiation of MeN(CH2-2-C6H4Br)2 with BunLi in thf
at -78 °C, followed by warming to room temperature and
addition of powdered Ph2BiBr, after careful workup gave
MeN(CH2-2-C6H4BiPh2)2 (4) as a pale yellow powder in
(9) Jura, M.; Levason, W.; Reid, G.; Webster, M. Dalton Trans. 2009,
7811.
(10) Davis, M. F.; Jura, M.; Levason, W.; Reid, G.; Webster, M.
J. Organomet. Chem. 2007, 692, 5589.
(11) (a) Wieber, M.; Rudolph, K. Z. Naturforsch., B 1988, 43, 739.
(b) Wieber, M.; Sauer, I. Z. Naturforsch., B 1985, 40, 1476.
(12) See the web site: Cordero, B.; Gomez, V.; Platero-Prats, A. E.;
Reves, M.; Echeverria, J.; Cremades, E.; Barragan, F.; Alvarez, S.
Dalton Trans. 2008, 2832 www.ccdc.cam.ac.uk/products/csd/radii.

Article
Organometallics, Vol. 30, No. 4, 2011 897
Figure 1. Structure of O{(CH2)2BiPh2}2 with the atom-number-
ing scheme. Ellipsoids are drawn at the 50% probability level, and
˚
H atoms are omitted for clarity. Selected bond lengths (A) and
Figure 3. Structure of S(CH2-2-C6H4BiPh2)2 with the atom-
numbering scheme. Ellipsoids are drawn at the 50% probability
level, and H atoms are omitted for clarity. Selected bond lengths
angles (deg): Bi1-C1 = 2.254(5), Bi1-C7 = 2.264(5), Bi1-
C13 = 2.280(5), Bi2-C17 = 2.256(5), Bi2-C23 = 2.258(5),
Bi2-C16 = 2.262(5), O1-C14=1.430(6), O1-C15=1.421(6),
Bi1 O1 = 3.203(3), Bi2 O1 = 3.126(3); C-Bi-C=89.89-
˚
(A) and angles (deg): Bi1-C1=2.249(5), Bi1-C7 = 2.267(4),
Bi1-C13=2.275(4), Bi1 S1=3.3254(12), Bi2-C26=2.272(4),
3 3 3
3 3 3
3 3 3
(17)-95.27(19), C15-O1-C14=112.1(4).
Bi2-C27
=
2.246(4), Bi2-C33 = 2.259(4), Bi2 S1 =
3 3 3
3.3013(12), S1-C19=1.805(5), S1-C20 =1.811(5); C1-Bi1-
C7 = 97.0(2), C1-Bi1-C13 = 92.84(15), C7-Bi1-C13 =
94.06(15), C27-Bi2-C33 = 92.7(2), C27-Bi2-C26=94.9(2),
C33-Bi2-C26 = 94.86(15), C19-S1-C20 = 101.4(2), Bi2
3 3 3
S1 Bi1 = 147.84(4).
3 3 3
in ∼20% yield. The identity in this case was confirmed by the
1H and 13C{1H} NMR spectra, which, in addition to the
diagnostic resonances associated with the -C6H4CH2N-
(Me)CH2C6H4- linker, showed singlet Me2Bi resonances
at δ 1.1 (1H) and δ 2.91 (13C{1H}). The FAB mass spectrum
shows [P]þ and [P - Me]þ. Careful examination of the NMR
spectra showed that some samples contain small amounts
(<5%) of a second species, which was identified as the small-
ring azabismocine MeN(CH2-2-C6H4)2BiMe (7), i.e. the Me-
substituted analogue of 5, which may result either from
scrambling or from some MeBiBr2 in the bismuth reagent.
The sulfur-bridged ligand S(CH2-2-C6H4BiPh2)2 (9) was
obtained similarly from S(CH2-2-C6H4Br)2, MeLi, and
Ph2BiBr as a white solid in 33% yield. The NMR and FAB
mass spectra are consistent with the formulation (Experi-
mental Section), and in this case white crystals were obtained
from toluene solution. The structure (Figure 3) again shows a
pyramidal BiC3 unit, with angles consistent with predomi-
nantly Bi 6p character in the Bi-C bonds.2b,6 There are
Figure 2. Structure of MeN(CH2-2-C6H4)2BiBr with the atom-
numbering scheme. Ellipsoids are drawn at the 50% probability
level, and H atoms are omitted for clarity. Selected bond lengths
˚
(A) and angles (deg): Bi1-C1=2.251(6), Bi1-C15=2.240(6),
Bi1 N1 = 2.503(5), Bi1-Br1=2.8007(7), N1-C7=1.479(7),
3 3 3
N1-C8=1.476(7), N1-C9 = 1.472(7); C15-Bi1-C1 = 99.1(2),
C15-Bi1-N1=73.9(2), C1-Bi1-N1 = 72.3(2), C15-Bi1-Br1
=93.4(2), C1-Bi1-Br1=91.43(15), N1-Bi1-Br1=157.00(11).
modest yield (27%). The identity of the product was confirmed
1
by the H and 13C{1H} NMR spectra, the latter showing
resonances at δ 42.21 (CH3N) and 66.95 (CH2N) and 10
distinct aromatic carbon resonances, including two assigned
as BiCipso. The CI mass spectrum showed the highest signifi-
cant ion at m/z 857, corresponding to [P - Ph]þ. A small
amount of white crystalline material isolated from the diethyl
ether solution of the crude ligand was found to be the small-
ring bromoazabismocine MeN(CH2-2-C6H4)2BiBr (5), which
probably arises from some residual BiBr3 impurity in the
Ph2BiBr. The structure (Figure 2) is similar to that in other
azabismocines8m and shows a distorted-trigonal-bipyramidal
geometry about bismuth with a vacant equatorial vertex. The
hypervalent Bi .S interactions involving both bismuth cen-
3 3 3
˚
ters, Bi(1) S(1)=3.3254(12) A, Bi(2) S(1)=3.3013(12) A,
˚
3 3 3
3 3 3
and Bi(2) S(1) Bi(1) = 147.84(4)°; the Bi S inter-
3 3 3
3 3 3
3 3 3
actions are, as expected, significantly longer than in thiabis-
mocines containing a single hypervalent link, which are typi-
cally <3.0 A,8m but are still well within the sum of the van der
˚
12
Waals radii (3.8 A). The corresponding dimethylbismuth
˚
ligand S(CH2-2-C6H4BiMe2)2 (10) was obtained similarly
to 9, although in rather poor yield, as a very air-sensitive
yellow oil.
˚
The antimony analogue of 10, S(CH2-2-C6H4SbMe2)2 (11),
was obtained as an air-sensitive yellow oil in 68% yield, the
much higher yield being typical of ligands with stronger C-Sb
bonds, illustrating further the sensitivity of the C-Bi linkages.
Ligand 11 was thoroughly characterized by spectroscopy
(Experimental Section), and (in contrast with the bismuth
ligands) by quaternization with MeI to the distibonium salt
[S(CH2-2-C6H4SbMe3)2]I2 (11b). The structure of the latter
(Figure 4) confirms the identity of the parent ligand and also
hypervalent Bi(1) N(1) distance (2.503(5) A) lies at the
3 3 3
shorter end of the range in related complexes (2.517(4)-
2.764(5) A).
8m,13
˚
The corresponding reaction of MeN(CH2-2-C6H4Li)2
with Me2BiBr in thf, initially at -78 °C, followed by warm-
ing of the mixture to room temperature and workup, gave
MeN(CH2-2-C6H4BiMe2)2 (6) as an air-sensitive yellow oil
(13) Minora, M.; Kanamori, Y.; Miyake, A.; Akiba, K.-Y. Chem.
Commun. 1999, 861.
˚
reveals the hypervalent interaction Sb(1) S(1) = 3.555(2) A,
3 3 3

898 Organometallics, Vol. 30, No. 4, 2011
Benjamin et al.
Figure 5. Structure of the dication in [{CpFe(CO)2}2{O{(CH2)2-
SbMe2}2}][BF4]2 with the atom-numbering scheme. Ellipsoids
are drawn at the 50% probability level, and H atoms are omitted
Figure 4. Structure of the dication in [S(CH2-2-C6H4SbMe3)2]I2
with the atom-numbering scheme. Ellipsoids are drawn at the
50% probability level, and H atoms are omitted for clarity.
˚
for clarity. Selected bond lengths (A) and angles (deg): Fe1-
C9=1.788(12), Fe1-C10=1.784(12), Fe1-C(Cp)=2.065(11)-
2.096(11), Fe1-Sb1 = 2.4846(18), Fe2-C11 = 1.778(13),
Fe2-C12 = 1.799(14), Fe2-C(Cp) = 2.057(14)-2.091(13),
˚
Selected bond lengths (A) and angles (deg): Sb1-C1=2.094(6),
Sb1-C2 = 2.103(6), Sb1-C3 = 2.102(6), Sb1-C4 = 2.122(6),
Sb2-C17=2.106(6), Sb2-C18=2.097(6), Sb2-C19=2.094(6),
Sb2-C20 = 2.087(6), S1-C10 = 1.816(6), S1-C11 = 1.837(6),
Fe2-Sb2 = 2.4870(19), O1 Sb1 = 4.363(8), O1 Sb2 =
3 3 3
3 3 3
3.184(8); C9-Fe1-C10 = 95.9(5), C9-Fe1-Sb1 = 93.4(4),
C10-Fe1-Sb1 = 90.5(4), C11-Fe2-C12 = 95.4(5), C11-
Fe2-Sb2 = 94.1(4), C12-Fe2-Sb2 = 88.1(4).
Sb1 S1 = 3.554; C1-Sb1-C2 = 110.7(2), C1-Sb1-C3 =
3 3 3
106.5(3), C2-Sb1-C3=106.6(2), C1-Sb1-C4=117.3(3), C3-
Sb1-C4=103.8(2), C2-Sb1-C4=111.0(2), C19-Sb2-C20=
111.8(3), C18-Sb2-C19=109.2(2), C18-Sb2-C20=108.3(2),
C17-Sb2-C18 = 106.9(2), C17-Sb2-C19 = 105.6(2), C17-
Sb2-C20=114.8(2), C10-S1-C11=99.4(3).
solutions. In contrast, the antimony ligand complexes were
prepared at room temperature and are more robust; no
significant scrambling of substituents or decomposition was
observed even after several hours in solution at room tem-
perature. The bismuthine complexes proved to be too unstable
at room temperature to obtain reproducible microanalyses,
and the purity of the products was therefore judged by
spectroscopic measurements on freshly prepared samples, an
approach used by other workers on metal bismuthine
complexes.5a,c,d In contrast, microanalytical data on the stibine
complexes were obtained without problems. The fragility of
the hybrid dibismuthine ligand complexes frustrated our
attempts to obtain X-ray crystal structures; however, two
structures of the complexed distibine analogues were obtained.
The structure of [{CpFe(CO)2}2{O{(CH2)2SbMe2}2}]-
[BF4]2 (18) (Figure 5) shows the antimony ligand bridging
two CpFe(CO)2 moieties via Sb, with the hypervalent interac-
˚
whereas Sb(2) S(1) = 4.419(2) A; the latter is significantly
3 3 3
˚
greater than the sum of the van der Waals radii (3.80 A). The
antimony analogues of 3, 6, and also O{(CH2)2SbMe2}2 have
been described previously.9,10
Complexes with [CpFe(CO)2]þ. The [dicarbonyl(η5-
cyclopentadienyl)iron]þ fragment was chosen as the Lewis acid
center to explore the coordination of these new bismuthine
ligands initially, since it provides a labile binding site (through
substitution of the thf ligand in [CpFe(CO)2(thf)]þ) likely to be
required for substitution by the bismuthine and contains
several reporter groups in the IR and NMR spectra, and also
two polymorphs of the relatively stable [CpFe(CO)2(BiPh3)]-
BF4 have been characterized by X-ray crystallography pre-
viously, providing an experimental comparison for the present
work.5a,6
˚
tion O Sb(2) = 3.184(8) A, whereas the O Sb(1) distance
3 3 3
3 3 3
˚
is 4.363(8) A, showing no interaction (van der Waals radii sum
The syntheses involved generation of [CpFe(CO)2(thf)]BF4
initially from [CpFe(CO)2I], thf, and AgBF4, in anhydrous
CH2Cl2 solution (the weak donor bismuthine ligands do not
coordinate to the iron in the presence of a large excess of thf,
e.g. in thf solution, nor do they displace the iodide from the
starting material directly).5a The temperature at which the
reaction is carried out is also critical; for ligands containing
Me2Bi- donor groups a CH2Cl2 solution of the ligand was
added to a solution of [CpFe(CO)2(thf)]BF4 in anhydrous
CH2Cl2 at -78 °C and the mixture was stirred overnight, as it
was slowly warmed to near-ambient temperature. The com-
plex was then quickly isolated and stored in a freezer at -18 °C,
although even in a freezer slow decomposition occurs (over
a few days). If the reaction was carried out at room tempera-
ture, there was extensive decomposition, some black solid
precipitate formed (Bi?), and scrambling of the groups on
the bismuth center was observed. In contrast, those ligands
containing Ph2Bi- groups did not react with a solution of
[CpFe(CO)2(thf)]BF4 in anhydrous CH2Cl2 at -78 °C, and
hence the reactions were conducted at room temperature.
These complexes were much less prone to decomposition,
although measurements were always made on freshly prepared
˚
3.60 A). There are no significant differences in the bond lengths
of the two iron units, which suggests that the hypervalent
interaction is weak and does not lead to significant differences
in the electronic environment at the metal centers.
The structure of [{CpFe(CO)2}2{MeN(CH2-2-C6H4Sb-
Me2)2}][BF4]2 (17) (Figure 6) again shows the ligand coordi-
nated via antimony to two [CpFe(CO)2]þ units, and in this case
˚
there is no hypervalent interaction (Sb N > 4.85 A);the
3 3 3
˚
sum of the van der Waals radii in this case is 3.74 A.
Presumably in this case the small energy gain to be made by
a hypervalent interaction, which would require some confor-
mational change in the molecule, is less than the energy
obtained from packing the molecules in the form found.
The key spectroscopic data for the complexes are summar-
ized in Table 1, the NMR data for the bismuthine complexes
being recorded at 223 K to slow decomposition in solution.
Apart from those for [{CpFe(CO)2}2{MeN(CH2-2-C6H4Bi-
Ph2)2}][BF4]2 (15), discussed below, the solution spectroscopic
data are generally similar, with δ(13C) of the Cp carbons and
the CO groups covering small ranges, although for directly
comparable compounds the carbonyl resonances are at higher

Article
Organometallics, Vol. 30, No. 4, 2011 899
frequency in the bismuthine systems compared to in the
stibines, consistent with weaker donation by the former. The
twocarbonyl stretching frequencies (A1 þ B1) ofthecomplexes
in CH2Cl2 solution show decreases of between 10 and 20 cm-1
on replacing Bi by Sb in comparable ligand frameworks,
showing the usual trends in group 15 ligand chemistry.2,5
Much more interesting are the IR spectra in the carbonyl
region, recorded as Nujol mulls (Table 1). All of the
dibismuthine ligand complexes and the two distibine com-
plexes 18 and 19 show three or four carbonyl stretching
vibrations, consistent with the presence of inequivalent iron
centers resulting from hypervalent interactions (four stretches
are expected;where only three are observed, this is attributed
to accidental coincidence). In contrast, complexes 17 and 20
show only two carbonyl stretching vibrations, due to the
absence of hypervalent interactions (confirmed for 20 by the
X-ray structure above). The model complex [{CpFe(CO)2}2-
{Ph2Sb(CH2)3SbPh2}][BF4]2 (22), which contains no hetero-
atom to make a hypervalent contact, has an IR spectrum in
the carbonyl region very similar to those of 17 and 20,
confirming this deduction. The presence of inequivalent iron
centers in some of the solid complexes due to hypervalency,
which appears to be lost in solution, is further evidence for the
weakness of the hypervalent coordination. The complex
[{CpFe(CO)2}2{MeN(CH2-2-C6H4BiPh2)2}][BF4]2 (15) is un-
ique in this series in that it shows hypervalent interactions
both as the solid and in solution in CH2Cl2. In addition to
the presence of four ν(CO) bands in the solution IR spectrum,
the 13C{1H} NMR spectrum at 223 K shows two carbonyl
resonances and two very closely spaced Cp resonances of
equal intensity. This is readily explained by a hypervalent
N
Bi interaction involving one bismuth center which is
3 3 3
retained in solution. Why this complex alone should show the
retention of the hypervalent interaction in solution is less
clear. The data in Table 1 show that hypervalence is more
common (and presumably a stronger interaction) in bismuth
systems compared with antimony, but whether the interaction
remains in solution will depend upon small differences in
energy of the various ligand conformations possible in these
bridged systems, only some of which are suitably oriented to
retain the interaction. In contrast to the uncomplexed ligand
structures described above, it seems that steric factors prevent
interaction of the heteroatom with both Sb and Bi centers in
the metal complexes.
[CpFe(CO)2L]BF4 (L = SbMe2Ph, BiPh2(o-C6H4OMe),
BiMe2Ph, BiPh3). As mentioned in the Introduction, almost
all known complexes of tertiary bismuthines contain the
symmetrically substituted monobismuthine ligands BiR3.
Since the hybrid dibismuthines described above contain two
different substituents at the bismuth, we also briefly explored
the reactions of BiPh2(o-C6H4OMe) and BiMe2Ph with the
þ
CpFe(CO2)2 acceptor group. [CpFe(CO)2(SbMe2Ph)]BF4
(21) was made as a model complex for comparison pur-
poses, and its structure (Figure 7) was determined. The
bond lengths and angles and the spectroscopic properties
are unexceptional, but notably, the complex is stable in
CH2Cl2 solution.
Figure 6. Structure of the dication in [{CpFe(CO)2}2{MeN-
(CH2-2-C6H4SbMe2)2}][BF4]2 1/2CH2Cl2 with the atom-num-
3
In contrast, the reaction of [CpFe(CO)2(thf)]þ with BiMe2Ph
under a variety of reaction conditions, e.g. performing the
reaction at temperatures varying from 195 K to ambient, in
the dark, and with different reaction times, gave red waxy solids
which were found by NMR spectroscopy and ESþ mass spec-
trometry (Experimental Section) to be mixtures containing all
possible R group combinations on bismuth: viz., [CpFe(CO)2-
(BiMe2Ph)]þ, [CpFe(CO)2(BiMe3)]þ, [CpFe(CO)2(BiMePh2)]þ,
bering scheme. Ellipsoids are drawn at the 50% probability
level, and H atoms are omitted for clarity. Selected bond lengths
˚
(A) and angles (deg): Fe1-Sb1=2.4669(14), Fe1-C6=1.777(10),
Fe1-C7 = 1.777(10), Fe1-C(Cp) = 2.081(10)-2.103(8), Fe2-
Sb2=2.4780(14), Fe2-C27=1.772(10), Fe2-C28=1.771(11),
Fe2-C(Cp) = 2.075(10)-2.101(9); C6-Fe1-C7=92.8(5), C6-
Fe1-Sb1 = 92.2(3), C7-Fe1-Sb1 = 91.2(3), C27-Fe2-C28 =
91.0(4), C27-Fe2-Sb2=91.9(3), C28-Fe2-Sb2 = 92.2(3).
Table 1. Selected Spectroscopic Data for [{CpFe(CO)2}nL][BF4]n
ν(CO)/cm-1
13C{1H} NMRa
complex
chlorocarbon soln
Nujol
δ(Cp)
86.3
δ(CO)
209.5
12
13
14
15
16
17
18
19
20
21
22
23
2063, 2020
2067, 2020
2072, 2020
2070, 2055, 2022, 1998
2071, 2024
2045, 2001
2044, 2000b
2050, 2006
2049, 2002
2046, 2002
2048, 2005
2057, 2001
2057, 2013
2065, 2019
2062, 2021, 2007 (sh)
2071, 2055, 2023
2068, 2015, 2005
2065, 2040, 2020, 2003
2071, 2043, 2017, 2004
2040, 1992
2041, 2034, 2005, 1993
2044, 2002 (sh), 1996
2039, 1998
2041, 1999
2042, 1992
2041, 2001
2044, 1997
85.3
86.2
85.4, 85.5
86.6
86.1
86.3
86.3
86.0
85.7
85.9
86.7
86.5
85.8
210.0
209.6
210.2, 211.1
209.6
209.7
210.7
209.2
209.0
209.3
208.9
209.4
209.3
208.9
24
[CpFe(CO)2(thf)][BF4]c
a Conditions: chlorocarbon solution, Bi ligand complexes at 223 K, Sb complexes at 295 K. b Spectrum recorded in MeCN due to poor solubility in
chlorocarbons. c Data from: Reger, D. L.; Coleman, C. J. Organomet. Chem. 1977, 131, 153.

900 Organometallics, Vol. 30, No. 4, 2011
Benjamin et al.
Conclusions
Preparative routes to a series of new hybrid dibismuthines
and distibines containing O-, N-, and S-donor atoms and
bearing either terminal phenyl or methyl substituents have
been developed. Reaction of these ligands with [CpFe-
(CO)2(thf)][BF4] leads to coordination via the Bi or Sb donor
atoms only, yielding ligand-bridged complexes. Spectroscopic
and structural studies reveal hypervalent Bi/Sb O/N/S in-
3 3 3
teractions in several of the ligands and also in all but two of the
complexes. The [CpFe(CO)2]þ fragment, which is bonded only
to Sb or Bi, has allowed us to probe the hypervalent O/N/
S
Sb/Bi interactions and particularly whether these are
3 3 3
Figure 7. Structure of the dication in [CpFe(CO)2(SbPhMe2)]-
[BF4] with the atom-numbering scheme. Ellipsoids are drawn at
the 50% probability level, and H atoms are omitted for clarity.
retained in solution. There is considerable disparity in the
strength of these interactions, from strong (and evident both in
the solid state and in solution) for [{CpFe(CO)2}2{MeN(CH2-
2-C6H4BiPh2)2}][BF4]2 to weaker (and only observed in
the solid state) in the other dibismuthine complexes, while
no hypervalency is evident in [{CpFe(CO)2}2{MeN(CH2-2-
C6H4SbMe2)2}][BF4]2 (X-ray and IR spectroscopic evidence)
or [{CpFe(CO)2}2{S(CH2-2-C6H4SbMe2)2}][BF4]2 (IR spec-
troscopic evidence). The bismuthine complexes also represent
the first examples with unsymmetrical substituents at Bi.
˚
Selected bond lengths (A) and angles (deg): Sb1-Fe1 =
2.4846(7), Fe1-C6=1.776(4), Fe1-C7=1.770(4), Fe-C(Cp)=
2.088(4)-2.118(4); C6-Fe1-C7 = 93.7(2), C6-Fe1-Sb1 =
89.10(13), C7-Fe1-Sb1=89.72(13).
Experimental Section
Infrared spectra were recorded as Nujol mulls between NaCl
plates using a Perkin-Elmer Spectrum 100 spectrometer over the
range 4000-500 cm-1, and solution spectra used NaCl solution
1
cells over the range 2200-1800 cm-1. H NMR spectra were
recorded from CDCl3 solutions using a Bruker AV300 spectro-
meter, and 1H and 13C{1H} NMR spectra of the complexes were
recorded from CDCl3 or CD2Cl2 solutions using a Bruker
DPX400 spectrometer and are referenced to the residual solvent
signal. NMR spectra of all of the ligands and antimony ligand
complexes were recorded at ambient temperature (295 K) unless
otherwise stated, but spectra of complexes of the bismuth
ligands were routinely run at 223 K, due to the limited solution
stability of these complexes, especially over the several hours
necessary to obtain 13C{1H} NMR data. Microanalyses on new
complexes were outsourced to Medac Ltd. The thermal instabil-
ity of the iron carbonyl complexes of the bismuth ligands
precluded outsourced microanalysis. FAB mass spectra (3-
NOBA matrix) were obtained from Medac Ltd. and positive
ion electrospray (ESþ) in MeCN solution using a VG Biotech
platform. Preparations were undertaken using standard Schlenk
and glovebox techniques under a N2 atmosphere. Solvents were
dried by distillation from CaH2 (CH2Cl2) or Na/benzophenone
ketyl (thf, hexane, and diethyl ether).
Figure 8. Structure of the dication in [CpFe(CO)2{BiPh2-
(o-C6H4OMe)}][BF4] 0.9CH2Cl2 with the atom-numbering
scheme. Ellipsoids are drawn at the 50% probability level, and
3
˚
H atoms are omitted for clarity. Selected bond lengths (A) and
angles (deg): Fe1-C1=1.780(7), Fe1-C2 = 1.776(7), Fe1-
C(Cp)= 2.072(6)-2.112(6), Fe1-Bi1 = 2.5631(9); C1-Fe1-
C2=92.2(3), C1-Fe1-Bi1=92.5(2), C2-Fe1-Bi1 = 91.6(2).
and [CpFe(CO)2(BiPh3)]þ. Reaction of [CpFe(CO)2(thf)]þ
with BiPh2(o-C6H4OMe) was more successful in that
[CpFe(CO)2{BiPh2(o-C6H4OMe)}]BF4 was isolated as
red crystals, although small amounts of [CpFe(CO)2-
{BiPh3-n(o-C6H4OMe)n}]BF4 (n = 0, 2, 3) were also de-
tected in the crude product and scrambling occurred when
CH2Cl2 solutions of [CpFe(CO)2{BiPh2(o-C6H4OMe)}]-
BF4 were allowed to stand. However, the crystal structure
of [CpFe(CO)2{BiPh2(o-C6H4OMe)}]BF4 was determined
and shows (Figure 8) the expected geometry; it is the first
crystallographically characterized example of a metal com-
plex with an unsymmetrically substituted monodentate bis-
muthine. In the course of this work we also reprepared
[CpFe(CO)2(BiPh3)]BF4 as red crystals, which proved to be
the dichloromethane solvate (1:1). There are no significant
differences in the bond lengths and angles about the Fe and
Bi in the present solvate compared to those in the two
published polymorphs.5a,6 The data are presented in the
Supporting Information.
O{(CH2)2SbR2}2 (R = Me, Ph),10 MeN(CH2-2-C6H4SbMe2)2,9
SbPh2Cl,14 SbMe2Ph,14 Ph2Sb(CH2)3SbPh2,15 BiMe2Ph,11b and
BiPh2(o-C6H4OMe)7b were made as described previously.
Ph2BiBr (1). Triphenylbismuth (29.8 g, 67.8 mmol) was
dissolved in diethyl ether (100 mL), and bismuth tribromide
(15.2 g, 33.9 mmol) in diethyl ether (100 mL) was added. The
reaction mixture was stirred for 16 h and concentrated to ∼20
mL, giving a pale yellow solid and a faintly yellow solution. The
solids were isolated by filtration and dried in vacuo. Yield: 14.3
g, 95%. 1H NMR (CDCl3): δ 7.3 (m, [2H], Ph), 7.6 (m, [4H], Ph),
8.1 (m, [4H], Ph). 13C{1H} NMR (CDCl3): δ 129.67, 132.79,
138.12 (Caromatic), 157.87 (BiCipso).
Me2BiBr (2). For all ligand preparations this was made and
used in situ. Bismuth bromide (3.0 g, 6.7 mmol) was dissolved in
(14) Levason, W.; Matthews, M. L.; Reid, G.; Webster, M. Dalton
Trans. 2004, 51.
(15) Sato, S.; Matsumura, Y.; Okawara, R. J. Organomet. Chem.
1972, 43, 333.

Article
Organometallics, Vol. 30, No. 4, 2011 901
Table 2. Crystal Data and Structure Refinement Detailsa
{O(CH2)2BiPh2}2 (3)
28H28Bi2O
798.46
MeN(CH2-2-C6H4)2BiBr (5)
S(CH2-2-C6H4BiPh2)2 (9)
[S(CH2-2-C6H4SbMe3)2]I2 (11b)
formula
Mw
C
C15H15BiBrN
498.17
monoclinic
P21/n (No. 14)
8.2155(10)
12.371(2)
13.950(2)
90
95.362(10)
90
1411.6(4)
4
15.30
21 119
3238
0.068
154, 0
0.036
0.048
0.069
0.074
C38H32Bi2S
938.66
C20H30I2SSb2
799.80
monoclinic
P21/n (No. 14)
12.047(2)
8.0567(15)
26.471(5)
90
100.379(7)
90
2527.1(8)
4
4.67
21 722
5737
0.036
232, 0
0.043
0.055
0.084
0.090
cryst syst
space group
triclinic
P1 (No. 2)
8.0582(10)
10.6596(15)
15.370(2)
81.788(10)
86.311(10)
73.351(10)
1251.6(3)
2
14.06
26 661
5713
0.033
280, 0
0.027
0.041
0.048
0.053
monoclinic
P21/n (No. 14)
11.2692(10)
12.8951(10)
22.4136(15)
90
101.793(4)
90
3188.3(4)
4
11.11
45 794
7317
0.054
370, 0
0.029
0.037
0.058
0.061
˚
a (A)
˚
b (A)
˚
c (A)
R (deg)
β (deg)
γ (deg)
3
˚
U (A )
Z
μ(Mo KR) (mm-1
total no. of rflns
)
no. of unique rflns
Rint
no. of params, restraints
R1b (Io > 2σ(Io))
R1 (all data)
wR2b (Io > 2σ(Io))
wR2 (all data)
[{CpFe(CO)2}2{MeN-
(CH2-2-C6H4SbMe2)2}]-
[CpFe(CO)2{BiPh2-
(o-C6H4OMe)}]-
[BF4] 0.9CH2Cl2 (23)
3
[{CpFe(CO)2}2{{O(CH2)2-
SbMe2}2}][BF4]2 (18)
[CpFe(CO)2(SbPhMe2)]-
[BF4] (21)
[BF4]2 1/2CH2Cl2 (17)
3
formula
Mw
C
22H30B2F8Fe2O5Sb2
C33.5H38B2ClF8Fe2NO4Sb2
C15H16BF4FeO2Sb
492.69
C26.9H23.8BBiCl1.8F4FeO3
810.51
903.28
monoclinic
P21/n (No. 14)
8.0949(15)
14.664(3)
25.465(5)
90
96.009(10)
90
3006.2(10)
4
2.81
27 948
5858
0.089
370, 11
0.084
0.123
1082.92
triclinic
P1 (No. 2)
10.5977(10)
11.799(2)
16.732(3)
78.332(6)
86.814(8)
85.261(8)
2040.4(5)
2
cryst syst
space group
orthorhombic
P212121 (No. 19)
6.9012(10)
13.6533(15)
18.753(3)
90
90
90
1767.0(4)
4
2.39
15 822
4020
0.046
219, 0
0.030
0.034
triclinic
P1 (No. 2)
10.481(2)
12.3341(15)
12.370(3)
88.091(10)
66.197(10)
82.102(10)
1448.8(4)
2
6.78
29 158
6634
0.047
354, 22
0.044
˚
a (A)
˚
b (A)
˚
c (A)
R (deg)
β (deg)
γ (deg)
3
˚
U (A )
Z
μ(Mo KR) (mm-1
total no. of rflns
)
2.14
36 221
9355
0.064
500, 0
0.084
0.114
0.169
0.188
no. of unique rflns
Rint
no. of params, restraints
R1b (Io > 2σ(Io))
R1 (all data)
0.054
0.098
0.103
wR2b (Io > 2σ(Io))
0.144
0.162
0.071
0.074
wR2 (all data)
a
P
P
P
P
Common items: temperature 120 K; wavelength (Mo KR) 0.710 73 A; θ(max) = 27.5°. b R1 = ||Fo| - |Fc||/ |Fo|. wR2 = [ w(Fo2 - Fc2)2/
˚
4 1/2
wFo ] .
thf (40 mL) and the solution cooled to -78 °C, before the
dropwise addition of methyllithium (8.3 mL, 13.4 mmol, 1.6 M
solution in diethyl ether). The reaction mixture was stirred
(15 min, -78 °C) and then warmed to room temperature over
the course of 2 h, producing a faintly yellow solution. The
solvents were removed in vacuo, toluene (20 mL) was added,
and the mixture was filtered. The resulting pale yellow solution
was reduced in vacuo to give a yellow oil. Yield: 1.5 g, 70.3%. 1H
NMR (CDCl3): δ 1.9 (s, Me). 13C{1H} NMR (CDCl3): δ 27.77
(Me).
O{(CH2)2BiPh2}2 (3). Ph2BiBr (13.6 g, 31 mmol) was dissolved
in liquid ammonia (300 mL) at -78 °C. The addition of small
pieces of sodium (1.55 g, 67 mmol) with stirring for 15 min gave a
dark green solution. After 30 min the solution had become dark
red; a thf solution (10 mL) of bis(2-iodoethyl) ether (4.8 g, 15
mmol) was added and the ammonia slowly evaporated under a
flow of N2, leaving a dark solid residue. Extraction with diethyl
ether (60 mL) gave a pale yellow solution, which was reduced in
vacuo to yield an off-white crystalline powder. Yield: 6.5 g, 55%.
Anal. Calcd for C28H28Bi2O: C, 42.1; H, 3.5. Found: C, 42.1; H,
3.4. 1H NMR (CDCl3): δ 2.3 (t, [4H], CH2Bi), 4.1 (t, [4H], CH2O),
7.3 (m, [12H], Ph), 7.7 (m, [8H], Ph). 13C{1H} NMR (CDCl3): δ
34.13 (CH2Bi), 68.52 (CH2O), 127.26, 129.37, 137.26 (Caromatic),
148.92 (Cipso). FAB MS: m/z 286 [PhBi]þ, 363 [Ph2Bi]þ.
MeN(CH2-2-C6H4BiPh2)2 (4). MeN(CH2-2-C6H4Br)2 (1.75 g,
4.74 mmol) was dissolved in diethyl ether (60 mL) and cooled
to -78 °C, before the dropwise addition of nBuLi (6.42 mL, 9.96
mmol, 1.55 M solution in hexane). The reaction mixture was
stirred for 2 h before it was warmed slowly to room temperature.
BiPh2Br (4.3 g, 9.7 mmol) was added as a solid, and the mixture
was stirred at room temperaturefor 16 h. Degassed, distilled water
(60 mL) was added, and the organic layer was separated. The
aqueous phase was washed with diethyl ether (2 ꢀ 30 mL), and the
organic extracts were combined, dried over MgSO4, and filtered to
give a pale yellow solution. A small amount of white precipitate
formed, which was separated and identified as the small ring
MeN(CH2C6H4)2BiBr (5). The solvent was removed in vacuo,
giving an off-white/yellow solid. Yield: 1.2 g, 27%. Anal. Calcd for
C39H35Bi2N: C, 50.0; H, 3.8; N, 1.5. Found: C, 49.3; H, 3.2; N, 1.7.
1H NMR (CDCl3): δ 1.8 (s, [3H], MeN), 3.5 (s, [4H], CH2N),
7.1-7.8 (m, [28H], aromatic CH). 13C{1H} NMR (CDCl3): δ
42.21 (MeN), 66.95 (CH2N), 128.25, 128.49, 130.86, 131.09,
131.45, 138.30, 140.16, 144.81 (Caromatic), 157.2, 159.4 (BiCipso).
CI MS: m/z 857 [P - Ph]þ, 496 [Ph2Bi(C6H4)CH2N(Me)CH2]þ.

902 Organometallics, Vol. 30, No. 4, 2011
Benjamin et al.
[MeN(CH2-2-C6H4)2BiBr] (5). This species was isolated as a
minor byproduct from the preparation of 4 as a white powder.
Crystals of this material were grown from pentane solution. 1H
NMR (CDCl3): δ 2.8 (s, [3H], MeN), 4.0 (d, 2JHH = 15 Hz, [2H],
CHHN), 4.2 (d, 2JHH = 15 Hz, [2H], CHHN), 7.1-7.6 (m, [6H],
3,4,5-Ar), 8.7 (m, [2H], 2-Ar). 13C{1H} NMR (CDCl3): δ 44.30
(MeN), 65.94 (CH2N), 127.89, 128.27, 131.56, 140.27, 147.77
(Caromatic) (BiCipso unclear).
a saturated toluene solution. Yield: 1.5 g, 33%. Anal. Calcd for
C38H32Bi2S: C, 48.6; H, 3.4. Found: C, 48.5; H, 3.7. H NMR
1
(CDCl3):δ3.55(s,[4H], CH2S), 7.0-7.7(m,[28H], aromaticCH).
13C{1H} NMR (CDCl3): δ 40.74 (CH2S), 128.61, 128.83, 131.01,
131.40, 138.57, 138.72, 140.99, 144.15 (Caromatic), 157.19, 159.30
(BiCipso). FAB MS: m/z 961 [P þ Na]þ, 453 [C19H16Bi]þ, 421
[C14H12BiS]þ, 363 [Ph2Bi]þ, 286 [PhBi]þ.
S(CH2-2-C6H4BiMe2)2 (10). S(CH2-2-C6H4Br)2 (2.5 g,
6.72 mmol) was dissolved in diethyl ether (80 mL) and the solution
cooled to -30 °C, before the dropwise addition of n-butyllithium
solution (8.82 mL, 14.11 mol, 1.6 M solution in hexane). The
reaction mixture was stirred for 3 h at -18 °C, before the addition
of bromodimethylbismuth (2.58 g, 23.6 mmol in 80 mL of thf).
The resulting mixture was stirred overnight, during which time it
was warmed to room temperature, giving an orange solution and
some brown solid. The solvent was removed in vacuo, the residue
was redissolved in diethyl ether (80 mL), and this mixture was
filtered to give a yellow solution. Degassed, distilled water (60 mL)
was added and the organic layer extracted, before the aqueous
layer was washed with diethyl ether (2 ꢀ 10 mL). The combined
organic extracts were dried over MgSO4, and the solvent was
removed in vacuo, to give a yellow oil. Yield: 0.7 g, 15%. 1H NMR
(CDCl3): δ 1.15 (s, [12H], (MeBi)), 3.7 (s, [4H], CH2S), 7.1-7.9
(m, [8H], aromatic CH). 13C{1H} NMR (CDCl3): δ 3.94 MeBi,
42.54 (CH2S), 128.45, 129.63, 129.69, 138.47, 143.53 (Caromatic),
143.68 (BiCipso). CI MS: m/z 675 [P - Me]þ.
MeN(CH2-2-C6H4BiMe2)2 (6). MeN(CH2-2-C6H4Br)2 (3.57 g,
9.67 mmol) was dissolved in diethyl ether (50 mL) and cooled
to -78 °C, before the dropwise addition of nBuLi (12.1 mL,
19.4 mmol, 1.6 M solution in hexane). The reaction mixture was
stirred for 2 h before it was warmed slowly to room temperature,
producing a yellow solution. Simultaneously, Me2BiBr (6.79 g,
21.3 mmol) was prepared by the addition of methyllithium
(24.6 mL, 42.6 mmol, 1.7 M solution in diethyl ether) to a thf
(80 mL) solution of BiBr3 (9.55 g, 21.3 mmol), kept at -78 °C.
This mixture was stirred for 15 min at -78 °C and then warmed to
room temperature over 2 h. The two solutions were cooled
to -78 °C, combined, and stirred for 16 h, during which time it
was slowly warmed to room temperature. The solvent was
removed in vacuo. The solid residues were redispersed in diethyl
ether (80 mL), the mixture was filtered, and the resulting yellow
solution was treated with distilled, degassed water (60 mL). After
separation, the aqueous layer was washed with diethyl ether (2 ꢀ
20 mL). The combined organic extracts were dried over MgSO4
and filtered, and the solvent was removed to give a yellow oil.
Yield: 1.3 g, 19.6%. 1H NMR (CDCl3): δ 1.1 (s, [12H], MeBi), 1.9
(s, [3H], MeN), 3.5 (s, [4H], CH2N), 7.0-7.9 (m, [8H], aromatic
CH). 13C{1H} NMR (CDCl3): δ 2.91 (MeBi), 41.53 (MeN), 66.56
(CH2N), 127.20, 128.84, 136.00, 142.84, 147.71 (Caromatic), 168.81
(BiCipso). FAB MS: m/z 687 [P]þ, 672 [P - Me]þ, 433
[C16H18BiN]þ, 418 [C15H15BiN]þ.
S(CH2-2-C6H4SbMe2)2 (11). S(CH2-2-C6H4Br)2 (1.97 g, 5.31
mmol) was dissolved in diethyl ether (100 mL) and cooled in an
ice/ethanol bath (approximately -15 °C). nBuLi (6.64 mL of 1.6 M
in hexane, 10.62 mmol) was added dropwise. A bright yellow
precipitatewas formed and the mixturestirred for 3 h, maintaining
the temperature between -15 and 0 °C. A toluene solution
(60 mL) of SbMe2Cl (1.98 g, 10.62 mmol) was added dropwise
to the cooled lithiate, and the reaction mixture was stirred over-
night, resulting in a pale yellow solution and white precipitate.
Degassed water (100 mL) was added, and after thorough mixing
the organic layer was separated, the aqueous layer was washed
with diethyl ether (40 mL), and the combined organics were dried
over MgSO4. The solution was then filtered, and the volatiles were
MeN(CH2-2-C6H4)2BiMe (7). This species was also observed
as a minor byproduct present in some preparations of 6 (see text).
1H NMR (CDCl3): δ 1.15 (s, [3H], MeBi), 2.4 (s, [3H], MeN), 3.55
(d, 2JHH = 15 Hz, [2H], CHHN), 3.75 (d, 2JHH = 15 Hz, [2H],
CHHN), 7.0-7.3 (m, [6H], 3,4,5-Ar), 7.8 (m, [2H], 2-Ar). 13C{1H}
NMR (CDCl3): δ 42.04 (MeN), 61.94 (CH2N), 127.07, 127.65,
128.98, 136.61, 145.38 (Caromatic), (BiCipso unclear).
1
removed in vacuo, yielding a yellow oil. Yield: 3.8 g, 68%. H
S(CH2-2-C6H4Br)2 (8). 2-Bromobenzyl bromide (23.3 g,
0.092 mol) was dissolved in degassed absolute ethanol (300 mL),
and sodium sulfide nonahydrate (11.2 g, 0.047 mol) was added,
along with sodium hydroxide (four pellets). The reaction mixture
was refluxed for 16 h, giving a cream-colored precipitate and an
orange solution. The solvent was removed in vacuo, and the
resulting solids were treated with a mixture of diethyl ether
(200 mL) and degassed water (100 mL). The ether layer was
removed and the remaining solution washed with more diethyl
ether (2 ꢀ 60 mL). The combined organic extracts were dried over
MgSO4 before the majority of the solvent was removed in vacuo,
precipitating a pale yellow crystalline solid. Yield: 13.3 g, 78%. 1H
NMR (CDCl3): δ 3.8 (s, [4H], CH2S), 7.0 (t, [2H]), 7.2 (t, [2H]),
7.4 (d, [2H]), 7.5 (d, [2H], all aromatic CH). 13C{1H} NMR
(CDCl3): δ 36.48 (CH2S), 124.67, 127.48, 128.68, 130.77, 133.10,
137.29 (Caromatic).
S(CH2-2-C6H4BiPh2)2 (9). S(CH2-2-C6H4Br)2 (3.0 g, 8.06
mmol) was dissolved in diethyl ether (100 mL) and the solution
cooled to -30 °C, before the dropwise addition of n-butyllithium
solution (10.4 mL, 16.12 mmol, 1.55 M solution in hexane). The
reaction mixture was stirred for 3 h at -30 °C before the addition
of powdered BiPh2Br (7.14 g, 16.12 mmol) as a solid. The resulting
mixture was stirred overnight when it was slowly warmed to room
temperature, giving a yellow solution and some brown solid. The
solvent was removed in vacuo, and the solid was extracted with
toluene (80 mL) and the extract filtered, giving a yellow solution.
Degassed distilled water (60 mL) was added, the organic layer was
separated and dried over MgSO4, and the solvent was reduced in
volume to give a waxy yellow solid. Washing with degassed
acetone (2 ꢀ 10 mL) gave a white solid. Crystals were grown from
NMR (CDCl3): δ 0.9 (s, [12H], MeSb), 3.8 (s, [4H], CH2S),
7.1-7.6 (m, [8H], aromatic CH). 13C{1H} NMR (CDCl3): δ
-0.30 (MeSb), 40.15 (CH2S), 127.98, 128.77, 129.58, 135.32,
139.01, 144.02 (Caromatic).
S(CH2-2-C6H4SbMe3)2I2 (11b). A sample of the product (0.3 g)
was dissolved in acetone (10 mL), and excess MeI (2 mL) was
added. The mixture was stirred for 2 min and then allowed to
stand overnight, resulting in the formation of very pale yellow
needle crystals, which were isolated by filtration and dried in
vacuo. Anal. Calcd for C20H30I2SSb2: C, 30.0; H, 3.8. Found: C,
30.7; H, 3.8. 1H NMR (d6-dmso): δ 1.9 (s, [18H], MeSb), 3.8 (s,
[4H], CH2S), 7.4-7.8 (m, [8H], aromatic CH). 13C{1H} NMR (d6-
dmso): δ 4.9 (MeSb), 36.5 (CH2S), 128.4, 131.2, 131.5, 135.1,
141.3, 146.0 (Caromatic). ESþ MS: m/z 273 [C20H30Sb2S]2þ, 529
[C19H27Sb2S]þ.
[{CpFe(CO)2}2{O{(CH2)2BiPh2}2}][BF4]2 (12). [CpFe(CO)2I]
(0.15 g, 0.50 mmol) was dissolved in a mixture of CH2Cl2 (10 mL)
and thf (1 drop), and the resulting dark red-brown solution was
added to a CH2Cl2 (10 mL) solution of AgBF4 (0.098 g,
0.50 mmol) in a foil-wrapped flask. The reaction mixture was
stirred for 2 h before filtration. The red filtrate was cooled
to -78 °C, O{(CH2)2BiPh2}2 (0.2 g, 0.25 mmol) dissolved in
CH2Cl2 (10 mL) was added, and the mixture was stirred for 16 h,
warming slowly during this period. The solvent was removed in
vacuo, leaving a dark red solid which was stored in a freezer. Yield:
1
0.1 g, 30%. H (CDCl3, 223 K): δ 2.5 (s, [4H], CH2Bi), 4.25 (s,
[4H], CH2O), 5.3 (s, [10H], Cp), 7.3-7.8 (m, [20H], aromaticCH).
13C{1H} NMR (CDCl3, 223 K): δ 34.7 (CH2Bi), 69.3 (CH2O),
86.3 (Cp), 128.4, 131.2, 138.2 (Caromatic), 149.5 (BiCipso), 209.5
(CO). ESþ MS: m/z 975 [{CpFe(CO)2}{O{(CH2)2BiPh2}2}]þ. IR

Article
Organometallics, Vol. 30, No. 4, 2011 903
(Nujol/cm-1): 2062 (s), 2021 (s) 2007 (sh) (CO), 1090 (vbr) (BF4).
IR (CHCl3/cm-1): 2063 (s), 2020 (s) (CO).
42.8 (MeN), 62.2 (CH2N), 86.6 Cp, 127.7, 128.3, 129.5, 129.5,
137.3 (Caromatic), 146.0 (BiCipso), 209.6 CO. ESþ MS: m/z 523
[{CpFe(CO)2}2{S(CH2-2-C6H4BiPh2)2}][BF4]2 (13). [CpFe-
(CO)2I] (0.13 g, 0.43 mmol) was dissolved in a mixture of CH2Cl2
(10 mL) and thf (1 drop), and the resulting dark red-brown
solution was added to a CH2Cl2 (10 mL) solution of AgBF4
(0.083 g, 0.43 mmol) in a foil-wrapped flask. The reaction mixture
was stirred for 2 h before filtration. The red filtrate was cooled
to -78 °C, a solution of S(CH2-2-C6H4BiPh2)2 (0.2 g, 0.22 mmol),
dissolved in CH2Cl2 (10 mL), was added, and the mixture was
stirred for 16 h at room temperature. The solvent volume was
reduced (ca. 10 mL), and hexane (10 mL) was added, precipitating
a dark red-brown solid. After filtration, the residues were dried in
vacuo, yielding a dark red-brown waxy solid which was stored in a
[{CpFe(CO)2}2{MeN(CH2-2-C6H4BiMe2)2}]2þ
.
IR (Nujol/
cm-1): 2071 (s), 2043 (s), 2017 (s), 2004 (s) (CO), 1070 (vbr)
(BF4). IR (CH2Cl2/cm-1): 2071 (s), 2024 (s) (CO).
[{CpFe(CO)2}2{MeN(CH2-2-C6H4SbMe2)2}][BF4]2
(17).
This complex was preparted similarly to 15, using [CpFe(CO)2I]
(0.212 g, 0.70 mmol), AgBF4 (0.136 g, 0.70 mmol), and MeN-
(CH2-2-C6H4SbMe2)2 (0.15 g, 0.29 mmol). Reduction of the
solvent volume to ca. 5 mL and addition of hexane (5 mL)
precipitated the complex as a dark orange solid. Yield: 0.08 g,
26%. Crystals were grown from a CH2Cl2/hexane (1/1) mixture in
the refrigerator. Anal. Calcd for C33H37B2F4Fe2NO4Sb2: C, 38.1;
H, 3.6; N, 1.4. Found: C, 38.6; H, 3.8; N, 1.4. 1H NMR (CDCl3,
223 K): δ 1.9 (s, [12H], MeSb), 2.2 (s, [3H], MeN), 3.8 (s, [4H],
CH2N), 5.4 (s, [10H], Cp), 7.5-7.9 (m, [8H], aromatic CH).
13C{1H} NMR (CDCl3, 223 K): δ 2.2 (MeSb), 44.7 (MeN), 68.6
(CH2N), 86.1 (Cp), 129.5, 130.2, 131.1, 131.5, 132.3, 133.7
(Caromatic), 209.7 (CO). ESþ MS: m/z 434 [{CpFe(CO)2}2-
{MeN(CH2-2-C6H4SbMe2)2}]2þ. IR (Nujol/cm-1): 2040 (s),
1992 (s) (CO), 1080 (vbr) (BF4). IR (CHCl3/cm-1): 2045 (s),
2001 (s) (CO).
[{CpFe(CO)2}2{O{(CH2)2SbMe2}2}][BF4]2 (18). This com-
plex was prepared similarly to 15 from [CpFe(CO)2I] (0.162 g,
0.53 mmol), AgBF4 (0.103 g 0.53 mmol), and O{(CH2)2SbMe2}2
(0.100 g, 0.27 mmol). The crude dark orange solid was dissolved in
CH2Cl2, and after 10 min of stirring a pale orange powder
precipitated out and was isolated by filtration. Yield: 0.043 g,
18%. Pale orange platelike crystals were grown from the filtrate.
1
freezer. Yield: 0.05 g, 16%. H NMR (CDCl3, 223 K): δ 3.7 (s,
[4H], CH2S), 5.28 (s, [10H], Cp), 7.3-7.9 (m, [28H], aromatic
CH). 13C{1H} NMR (CDCl3 223 K): δ 46.2 (CH2S), 85.3 (Cp),
128.3, 128.9, 131.0, 131.9, 132.0, 138.0, 138.2 (Caromatic), 152.1,
156.7 (BiCipso), 210.0 (CO). ESþ MS: m/z 1116 [CpFe(CO)2-
{S(CH2-2-C6H4BiPh2)2]þ, 647 [{CpFe(CO)2}2{S(CH2-2-C6H4-
BiPh2)2}]2þ. IR (Nujol/cm-1): 2071 (s), 2055 (s), 2023 (s) (CO),
1080 (vbr) (BF4). IR (CH2Cl2/cm-1): 2067 (s), 2020 (s) (CO).
[{CpFe(CO)2}2{S(CH2-2-C6H4BiMe2)2}][BF4]2 (14). [CpFe-
(CO)2I] (0.176 g, 0.58 mmol) was dissolved in a mixture of CH2Cl2
(10 mL) and thf (1 drop), and the resulting dark red-brown
solution was added to a CH2Cl2 (10 mL) solution of AgBF4
(0.113 g, 0.58 mmol) in a foil-wrapped flask. The reaction mixture
was stirred for 2 h before filtration. The red filtrate was cooled
to -78 °C, a solution of S(CH2-2-C6H4BiMe2)2 (0.2 g, 0.29
mmol), dissolved in CH2Cl2 (10 mL), was added, and the mixture
was stirred for 16 h at -78 °C. The solvents were removed in
Anal. Calcd for C22H30B2F8Fe2O5Sb2 CH2Cl2: C, 28.0; H, 3.3.
3
Found: C, 27.4; H, 3.0. 1H NMR (CD3CN): δ 1.5(s, [12H], MeSb)
2.4 (t, [4H], CH2Sb) 3.8 (t, [4H], CH2O), 5.3 (s, [10H], Cp), 5.5
(CH2Cl2). 13C{1H} NMR (CD3CN): δ -0.9 (MeSb), 19.8
(CH2Sb), 67.8 (CH2O), 86.3 (Cp), 210.7 (CO). ESþ MS: m/z
817 [{Cp(CO)2Fe}2{O{(CH2)2SbMe2}2}BF4]þ. IR (Nujol/cm-1):
2041 (s), 2034 (s), 2005 (s), 1993 (s) (CO), 1080 (vbr) (BF4). IR
(MeCN/cm-1): 2044 (s), 2000 (s) (CO).
1
vacuo, leaving a dark red solid. Yield: 0.15 g, 42%. H NMR
(CDCl3, 223 K): δ 1.76 (s, [12H], MeBi), 3.44 (s, [4H], CH2S), 5.41
(s, [10H], Cp), 7.4-8.2 (m, [8H], aromatic CH). 13C{1H} NMR
(CDCl3, 223 K): δ 7.2 (MeBi), 46.2 (CH2S), 86.2 (Cp), 128.2,
129.0, 131.8, 132.2, 138.2 (Caromatic), 144.5 (BiCipso), 209.6 (CO).
ESþ MS: m/z 523 [{CpFe(CO)2}2{S(CH2-2-C6H4BiMe2)2}]2þ. IR
(Nujol/cm-1): 2068 (s), 2015 (s), 2005 (s) (CO), 1085 (vbr) (BF4).
IR (CH2Cl2/cm-1): 2072 (s), 2025 (s) (CO).
[{CpFe(CO)2}2{O{(CH2)2SbPh2}2}][BF4]2 (19). This complex
was prepared similarly to 18 from [CpFe(CO)2I] (0.195 g, 0.641
mmol), AgBF4 (0.125 g, 0.641 mmol), and O{(CH2)2SbPh2}2
(0.200 g, 0.321 mmol). The addition of hexane to the reaction
mixture precipitated an orange solid. Yield: 0.20 g, 54%. Anal.
[{CpFe(CO)2}2{MeN(CH2-2-C6H4BiPh2)2}][BF4]2 (15). [CpFe-
(CO)2I] (0.13 g, 0.43 mmol) was dissolved in a mixture of CH2Cl2
(10 mL) and thf (1 drop), and the resulting dark red-brown
solution was added to a CH2Cl2 (10 mL) solution of AgBF4
(0.083 g, 0.43 mmol) in a foil-wrapped flask. The reaction mixture
was stirred for 2 h before filtration. A solution of MeN(CH2-2-
C6H4BiPh2)2 (0.2 g, 0.21 mmol) dissolved in CH2Cl2 (10 mL) was
added and the mixture stirred for 16 h at room temperature. The
solvent volume was reduced (to ca. 10 mL), and hexane (10 mL)
was added, producing a waxy red-brown solid and a light brown-
yellow solution. After filtration, the residues were dried in vacuo,
giving a dark brown-red solid which was stored in a freezer. Yield:
0.08 g, 26%. 1H NMR (CDCl3, 223 K): δ 3.1 (s, [3H], MeN), 4.5
(s, [2H] CH2N), 4.6 (s, [2H], CH2N), 5.18 (s, [5H], Cp), 5.19 (s,
[5H] Cp), 7.1-7.8 (m, [28H], aromatic CH). 13C{1H} NMR
(CDCl3, 223 K): δ 45.8 (MeN), 68.5, 68.6 (CH2N), 85.44, 85.47
(Cp), 128.3, 128.9, 129.4, 131.0, 131.6, 132.4, 136.4, 137.4, 138.1
(Caromatic), 150.6, 151.2, 155.5 (BiCipso), 210.2, 211.1 (CO). IR
(Nujol/cm-1): 2065 (s), 2040 (s), 2020 (s), 2003(s) (CO), 1084 (vbr)
(BF4). IR (CH2Cl2/cm-1): 2070 (s), 2055 (s), 2022 (s), 1998 (s)
(CO).
[{CpFe(CO)2}2{MeN(CH2-2-C6H4BiMe2)2}][BF4]2 (16). This
complex was prepared by a method similar to that for 13, using
[CpFe(CO)2I] (0.13 g, 0.44 mmol), AgBF4 (0.085 g, 0.44 mmol),
and MeN(CH2-2-C6H4BiMe2)2 (0.15 g, 0.22 mmol). The reaction
mixture was kept at -78 °C throughout. After the mixture was
stirred for 16 h, the solvent was removed in vacuo, producing a
waxy red-brown solid, which was stored in a freezer. Yield: 0.03 g,
13%. 1H NMR (CDCl3, 223 K): δ 1.4 (s, [12H], MeBi), 1.85 (s,
[3H], MeN), 3.5 (s, [4H], CH2N), 5.4 (s, [10H], Cp), 7.3-8.2 (m,
[8H], aromatic CH). 13C{1H} NMR (CDCl3, 223 K):δ5.9 (MeBi),
Calcd for C42H38B2F8Fe2O5Sb2 2CH2Cl2: C, 40.0; H, 3.2. Found
3
C 39.2, H, 3.6. 1H NMR (CDCl3): δ 2.9 (t, [4H], CH2Sb), 3.6 (t,
[4H], CH2O), 5.3 (CH2Cl2), 5.5 (s, [10H], Cp), 7.4-7.6 (m, [20H],
aromatic CH). 13C{1H} NMR (CDCl3): δ 22.1 (CH2Sb), 67.2
(CH2O), 86.3 (Cp), 128.0, 130.9, 132.2, 135.2 (Caromatic), 209.2
(CO). ESþ MS: m/z
= 1063 [{Cp(CO)2Fe}2{O{(CH2)2-
SbPh2}2}BF4]þ. IR (Nujol/cm-1): 2044 (s), 2002 (sh), 1996 (s)
(CO), 1080 (vbr) (BF4). IR (CH2Cl2/cm-1): 2050 (s), 2006
(s) (CO).
[{CpFe(CO)2}2{S(CH2-2-C6H4SbMe2)2}][BF4]2 (20). This
complex was prepared similarly to 18, from [CpFe(CO)2I]
(0.177 g, 0.58 mmol), AgBF4 (0.113 g, 0.58 mmol), and S(CH2-
2-C6H4SbMe2)2 (0.150 g, 0.29 mmol). The title compound was
isolated as an orange solid by precipitation with n-hexane from a
CH2Cl2 solution. Yield: 0.39 g, 37%. Anal. Calcd for C32H34-
B2F8O4Fe2SSb2: C, 35.1; H, 3.2. Found: C, 35.3; H, 3.0. 1H NMR
(CD2Cl2): δ 1.9 (s, [12H], MeSb, 3.9 (s, [4H], CH2S), 5.4 (s, [10H],
Cp), 7.3-7.7 (m, [8H], aromatic CH). 13C{1H} NMR (CD2Cl2):
δ -2.7 (MeSb), 38.1 (CH2S), 86.0 (Cp), 129.4, 129.6, 132.0, 132.3,
135.0, 142.1 (Caromatic), 209.0 (CO). ESþ MS: m/z 957
[{CpFe(CO)2}2{S(CH2-2-C6H4SbMe2)2}BF4]þ, 435 [{CpFe-
(CO)2}2{S(CH2-2-C6H4SbMe2)2}]2þ. IR (Nujol/cm-1): 2039 (s),
1998 (s) (CO), 1080 (vbr) (BF4). IR (CH2Cl2/cm-1): 2049 (s), 2002
(s) (CO).
[CpFe(CO)2(PhSbMe2)][BF4] (21). This complex was prepared
similarly to 18, using [CpFe(CO)2I] (0.096 g, 0.316 mmol), AgBF4
(0.062 g, 0.316 mmol), and SbPhMe2 (0.072 g, 0.316 mmol). The
additionofhexane(ca. 10mL) tothe reactionmixtureprecipitated

904 Organometallics, Vol. 30, No. 4, 2011
Benjamin et al.
a pale orange-pink powder. Yield: 0.05 g, 32%. Crystals were
grown from a CH2Cl2/hexane (1/1) mixture in the refrigerator.
Anal. Calcd for C15H16BF4FeO2Sb: C, 36.6; H, 3.3. Found: C,
35.8; H, 3.2. 1H NMR (CDCl3, 223 K): δ 1.9 (s, [6H], MeSb), 5.4
(s, [5H], Cp), 7.6 (m, [5H], aromatic CH). 13C{1H} NMR (CDCl3,
223 K): δ 0.8 (MeSb), 85.7 (Cp), 128.7, 130.5, 131.8, 133.7
(Caromatic), 209.3 (CO). ESþ MS: m/z 405 [CpFe(CO)2-
(PhSbMe2)]þ. IR (Nujol/cm-1): 2041 (s), 1999 (s) (CO), 1080
(vbr) (BF4). IR (CH2Cl2/cm-1): 2046 (s), 2002 (s) (CO).
CH2Cl2 (10 mL) and thf (1 drop) and the resulting dark red-
brown solution added to a CH2Cl2 (10 mL) solution of AgBF4
(0.061 g, 0.316 mmol) in a foil-wrapped flask. The reaction
mixture was stirred for 2 h, before filtration, to give a dark
red solution, which was cooled to -78 °C. BiPhMe2 (0.10 g,
0.32 mmol) dissolved in CH2Cl2 (10 mL) was added, and the
mixture was stirred at -78 °C for 1 h. A 2 mL aliquot was then
removed for NMR analysis. The remaining reaction mixture
was stirred at -78 °C for 18 h, and a second 2 mL aliquot was
removed for NMR analysis. The remaining solvent was re-
moved in vacuo, to give a dark red solid. Selected spectroscopic
data on the Fe-containing product (asterisks denote the major
species present) are as follows. First aliquot: 1H NMR (CDCl3,
223 K) δ 1.12 (s, Me3Bi), 1.275 (s, Me2BiPh)*, 1.45 (MeBiPh2)*,
5.20, 5.40*, 5.42*, 5.60 (Cp), 7.38-7.89 (aromatic CH); 13C{1H}
NMR (CDCl3, 223 K) δ -6.16 (BiMe3), 1.73 (BiMe2Ph)*,
3.36 (BiMePh2)*, 85.47*, 85.73*, 86.20 (Cp), 127.95-147.50
(Caromatic), 209.6, 210.0 (CO); EIþ MS m/z 618 [CpFe-
(CO)2(BiPh3)]þ, 555 [CpFe(CO)2(BiPh2Me)]þ, 493 [CpFe-
(CO)2(BiPhMe2)]þ, 431 [CpFe(CO)2(BiMe3)]þ.
[{CpFe(CO)2}2{Ph2Sb(CH2)3SbPh2}][BF4]2 (22). This com-
plex was prepared similarly to 18 from [CpFe(CO)2I] (0.103 g,
0.34 mmol), AgBF4 (0.066 g, 0.34 mol), and Ph2Sb(CH2)3SbPh2
(0.10 g, 0.17 mmol). The reaction mixture was reduced in volume
to ca. 10 mL, and the subsequent addition of hexane (5 mL)
precipitated a dark orange solid. Yield: 0.082 g, 43%. Anal. Calcd
for C41H36B2F8Fe2O4Sb2: C, 43.9; H, 3.2. Found: C, 43.3; H, 3.2.
1H NMR(CDCl3):δ1.9(m, [2H], CH2), 2.9(t, [4H], CH2Sb), 5.4 (s,
[10H], Cp), 7.4-7.5 (m, [20H], aromatic CH). 13C{1H} NMR
(CDCl3): δ 22.5 (CH2Sb), 23.7 (CH2), 85.9 (Cp), 127.1, 130.7,
132.0, 134.9 (Caromatic), 208.9 (CO). ESþ MS: m/z 474 [{CpFe-
(CO)2}2{Ph2Sb(CH2)3SbPh2}]2þ. IR (Nujol/cm-1): 2042 (s), 1992 (s)
(CO), 1080 (br) (BF4). IR (CH2Cl2 /cm-1): 2048 (s), 2005 (s) (CO).
[CpFe(CO)2{Ph2Bi(o-C6H4OMe)}][BF4] (23). [CpFe(CO)2I]
(0.13 g, 0.425 mmol) was dissolved in a mixture of CH2Cl2 (10
mL) and thf (1 drop), and the resulting dark red-brown solution
was added to a CH2Cl2 (10 mL) solution of AgBF4 (0.083 g, 0.425
mmol) in a foil-wrapped flask. The reaction mixture was stirred at
room temperature for 2 h before filtration to give a red solution. A
solution of BiPh2(o-C6H4OMe) (0.3 g, 0.43 mmol, dissolved in
10 mL of CH2Cl2) was added and the mixture stirred for 1 h. The
solvent was removed in vacuo, and the residue was redissolved in
CH2Cl2 (20 mL) before further stirring for 18 h. Reduction of the
solvent volume to ca. 5 mL and the addition of hexane (5 mL)
precipitated the complex as a dark red-brown solid. Yield: 0.15 g,
20%. Crystals were grown from a CH2Cl2/hexane (1/1) mixture.
1H NMR (CDCl3, 223 K): δ 3.8 (s, [3H], OMe), 5.5 (s, [5H], Cp),
7.0-7.5 (m, [14H], aromatic CH). 13C{1H} NMR (CDCl3, 223
K): δ 56.5 (OMe), 86.5 (Cp), 114.4, 124.8, 128.4, 131.9, 133.6,
136.2, 146.0, 151.8 (Caromatic), 209.3 (CO). ESþ MS: m/z 647
[CpFe(CO)2{BiPh2(o-C6H4OMe)}]þ. IR (Nujol/cm-1): 2044 (s),
1997 (s) (CO), 1080 (vbr) (BF4). IR (CH2Cl2/cm-1): 2057 (s), 2013
(s) (CO). Note: the 1H and 13C{1H} NMR spectra always showed
weaker resonances, which were attributed to the presence of some
[CpFe(CO)2{BiPh3-n(o-C6H4OMe)n}][BF4] (n = 0, 2, 3), the
amounts varying from preparation to preparation. ESþ MS ions
were also seen at m/z 617 [CpFe(CO)2(BiPh3)]þ, 677 [CpFe(CO)2-
{BiPh(o-C6H4OMe)2}]þ,and707[CpFe(CO)2{Bi(o-C6H4OMe)3}]þ.
Reaction of [CpFe(CO)2(thf)]BF4 with BiPhMe2. [CpFe-
(CO)2I] (0.096 g, 0.316 mmol) was dissolved in a mixture of
The second aliquot was not significantly different. The final
solid isolated was only partially soluble in CDCl3, and the soluble
component seemed to contain [CpFe(CO)2(BiMe3-nPhn)]BF4
(n = 1-3), but no detectable amount of the BiMe3 complex.
X-ray Studies. Details of the crystallographic data collection
and refinement parameters are given in Table 2. Crystals were
obtained as described above. Data collection used a Nonius
Kappa CCD diffractometer fitted with monochromated
˚
(confocal mirrors) Mo KR X-radiation (λ = 0.710 73 A). Crystals
were held at 120 K under a nitrogen gas stream. Structure solution
and refinement were routine,16-18 with hydrogen atoms on C
added to the model in calculated positions and using the default
C-H distance.
CCDC reference numbers 797557-797565 contain the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgment. We thank the EPSRC for support
(EP/F038763) and Dr. M. Webster for assistance with the
X-ray crystallographic analyses.
Supporting Information Available: A table giving crystallo-
graphic details for the compound [CpFe(CO)2(BiPh3)]BF4
-
3
CH2Cl2, together with a figure of the structure, and CIF files for
the other crystal structures described. This material is available
free of charge via the Internet at http://pubs.acs.org.
(17) Sheldrick, G. M. SHELXL-97, Program for Crystal Structure
€
€
(16) Sheldrick, G. M. SHELXS-97, Program for Crystal Structure
€
Refinement; University of Gottingen, Gottingen, Germany, 1997.
(18) Flack, H. D. Acta Crystallogr., Sect. A 1983, 39, 876.
€
Solution; University of Gottingen: Gottingen, Germany, 1997.