9-Triptycenyl complexes of group 13 and 15 halides and hydrides

Article abstract of DOI:10.1016/j.jorganchem.2003.12.014

The reactions of 9-lithiotriptycene with AlCl₃, GaCl₃ and InBr₃ have been carried out and have yielded the complexes, [(tript)AlCl₂(OEt₂)], [(tript)GaCl₂(THF)] and [(tript)InBr(μ-Br)_2<

Full text of DOI:10.1016/j.jorganchem.2003.12.014

Journal of Organometallic Chemistry 689 (2004) 781–790
www.elsevier.com/locate/jorganchem
9-Triptycenyl complexes of group 13 and 15 halides and hydrides
*
Robert J. Baker, Markus Brym, Cameron Jones , Mark Waugh
Department of Chemistry, Cardiff University, P.O. Box 912, Park Place, Cardiff CF10 3TB, UK
Received 16 October 2003; accepted 10 December 2003
Abstract
The reactions of 9-lithiotriptycene with AlCl3, GaCl3 and InBr3 have been carried out and have yielded the complexes,
[(tript)AlCl2(OEt2)], [(tript)GaCl2(THF)] and [(tript)InBr(l-Br)2Li(OEt2)2], tript ¼ 9-triptycenyl. The latter two complexes have
been structurally characterised. The corresponding reactions of 9-lithiotriptycene with ECl3 (E ¼ P, As, Sb or Bi) afforded the
complexes, [(tript)ECl2], of which all but the phosphorus compound have been crystallographically authenticated. In addition,
the high yield syntheses of the thermally stable primary pnictanes [(tript)EH2] (E ¼ As, Sb) have been achieved by reaction of the
relevant halide complex with LiAlH4. The X-ray crystal structure of the antimony hydride complex is reported.
Ó 2003 Elsevier B.V. All rights reserved.
Keywords: Antimony; Arsenic; Triptycene; Hydride; Group 13; Group 15
1. Introduction
moiety in this respect, with the synthesis of the first
diphosphaalkyne, PBCC(C6H4)3CCBP [7]. The re-
markable thermal robustness of this air stable com-
pound has prompted us to investigate the use of the
9-triptycenyl ligand (tript) in the preparation of, for
example, group 13 diyl compounds, [(tript)MI:] and
transition metal terminal pnictinidene complexes,
[LnM ¼ E(tript)]. The most convenient precursors to
such compound types are the triptycenyl element diha-
lide or dihydride complexes, [(tript)EX2], E ¼ group 13
or 15 element, X ¼ halide or hydride.
The development of sterically bulky alkyl and aryl
ligands has facilitated the renaissance of interest in main
group chemistry that has occurred over the past 20
years. In group 15 this interest has largely revolved
around the kinetic stabilisation of novel low coordina-
tion and/or low oxidation state organo-pnicogen com-
pounds and their complexes, e.g., heteroalkynes, EBCR;
heteroalkenes, RE@CR2 [1], dipnictenes, RE@ER [2]
and pnictinidene complexes, LnM ¼ ER [3] (E ¼ group
15 element). In group 13, sterically demanding ligands
have most notably been employed to stabilise low oxi-
dation state compounds, e.g., metal(I) diyls RMI:
(M ¼ group 13 metal), which are finding wide use as
strong r-donor ligands in the formation of transition
metal complexes [4], the nature of the metal–metal
bonding in which is often a controversial issue [5].
We have a strong interest in low coordination and
low oxidation state group 13 [6] and 15 chemistry [2b]
and are keen to investigate the stabilising properties of
new ligand systems in these areas. We have recently
demonstrated the potential of the bulky triptycene
The synthesis and structural characterisation of the
primary phosphane member of this series, [(tript)PH2],
has previously been reported [8]. Very recently, this
work was extended to the low yield synthesis of the
corresponding arsane, [(tript)AsH2], though the stibane,
[(tript)SbH2], could not be prepared using the same
methodology [9]. It is noteworthy that the triptycenyl
ligand has also been employed in the preparation of
several group 14 complexes, e.g. [(tript)EH3] (E ¼ Si or
Ge) and [(tript)3GeCl] [10], the former of which are air
stable, whilst the steric properties of the 3-fold sym-
metric tript ligand in the latter has led to it being classed
as a molecular ‘‘gear’’. To the best of our knowledge
there have been no reports of triptycenyl complexes of
group 13 metals. Herein, we describe the synthesis and
* Corresponding author. Tel.: +44-29-20-874-060; fax: +44-29-20-
874-030.
E-mail address: jonesca6@cardiff.ac.uk (C. Jones).
structural characterisation of
a
series of such
0022-328X/$ - see front matter Ó 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2003.12.014

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R.J. Baker et al. / Journal of Organometallic Chemistry 689 (2004) 781–790
compounds, in addition to the preparation of several
triptycenyl-group 15 complexes. These include a rare
example of a structurally characterised primary stibane.
Mes ¼ C6H2Me3-2,4,6 [11], are monomeric in the solid
state, whilst bulkier ligands can lead to unsolvated
3-coordinate monomers, e.g., [(Mes*)AlCl2], Mes* ¼
C6H2But3-2,4,6 [12].
The molecular structure of complex 2 is depicted in
Fig. 1 and confirms it is monomeric. The gallium centre
has a distorted tetrahedral environment with Ga–Cl
bond lengths in the normal range [13]. Similarly, the
2. Results and discussion
2.1. Triptycenyl group 13 halide complexes
ꢀ
Ga–C distance of 1.978(7) A is very close to those ob-
served in related 3- and 4-coordinate, monomeric com-
ꢀ
plexes, e.g., 1.935(4) A in [(Mes*)GaCl2] [14] and
The reactions of 9-lithiotriptycene with AlCl3, GaCl3
or InBr3 in either diethyl ether or THF afforded the first
group 13-triptycenyl complexes, 1–3, in good yields
(Scheme 1). All three complexes appear to be indefinitely
stable in the air and are thermally robust. The spectro-
scopic data for each are consistent with their proposed
formulations, though a resonance for the carbon bear-
0
0
i
ꢀ
1.946(4) A in [(Ar )GaCl2(THF)], Ar ¼ C6H2Pr3-2,4,6
[11]. Interestingly, however, the Ga–O bond length in 2
ꢀ
[1.940(5) A] is significantly shorter than that in
0
ꢀ
[(Ar )GaCl2(THF)] [2.011(4) A], which is the only pre-
viously structurally characterised alkyl gallium dihalide
complex coordinated by an ether. This is especially
surprising as, intuitively, the tript ligand would be ex-
pected to be more sterically demanding than the Ar0 li-
gand and, therefore, should probably lead to a longer
Ga–O bond in 2. No explanation can be offered for this
observation at present.
ing the aluminium centre in 1 was not observed in its 13
C
NMR spectrum, probably due to the quadrupolar na-
ture of the metal. Both compounds 2 and 3 were shown
to be monomeric in the solid state by X-ray crystallog-
raphy (vide infra) but unfortunately X-ray quality
crystals of 1 could not be grown. Therefore, its degree of
association in the solid state cannot be certain and both
monomeric 4-coordinate or a dimeric 5-coordinate,
chloride-bridged complexes are possible. The low solu-
bility of this compound in non-coordinating organic
solvents prevented its solution molecular weight deter-
mination by normal methods. It is noteworthy, however,
that related, solvated aluminium complexes employing
moderately bulky aryl ligands, e.g., [(Mes)AlCl2(THF)],
The structure of 3 (Fig. 2) is related to that of 2 but it
exits as an ‘‘-ate’’ complex with a distorted tetrahedral
indium centre with one terminal bromide and two bro-
mides that bridge to the lithium centre. This can be
compared to [{(Me3Si)3C}InCl2(l-Cl)Li(THF)3] [15],
though in that case there is only one bridging halide.
ꢀ
The In–C bond length of 2.176(6) A in 3 is similar to
ꢀ
those in related 4-coordinate complexes, e.g., 2.17(2) A
1 M = Al, X = Cl, solv. = Et2O
2 M = Ga, X = Cl, solv. = THF
3 M = In, X = Br, solv. = LiBr(OEt2)2
MX2(solv.)
MX3, -LiX
Li
EH2
8 E = As
9 E = Sb
ECl3, -LiCl
LiAlH4
4 E = P
5 E = As
6 E = Sb
7 E = Bi
ECl2
Scheme 1.

R.J. Baker et al. / Journal of Organometallic Chemistry 689 (2004) 781–790
783
2.2. Triptycenyl group 15 halide complexes
The complexes [(tript)ECl2], E ¼ P 4, As 5, have been
previously prepared as in situ intermediates for the
preparation of [(tript)EH2] though no data were given in
those reports [8,9] and the complexes were not isolated.
In this study, 4, 5 and the heavier pnicogen analogues,
[(tript)ECl2], E ¼ Sb 6, Bi 7, were prepared in moderate
to good yields from the reactions of ECl3 (E ¼ P, As, Sb
and Bi) with one equivalent of 9-lithiotriptycene in THF
(Scheme 1). All complexes are thermally very robust and
appear to be indefinitely stable in air in the solid state.
The spectroscopic data for the complexes are consistent
with their proposed structures which in the cases of 5–7
were confirmed by X-ray crystallographic analyses.
The molecular structures of each (Figs. 3–5) show
them to be monomeric and isostructural, though none
are isomorphous. In all, the pnicogen centre is signifi-
cantly distorted from a trigonal geometry with the de-
gree of pyramidalisation increasing in the series (R
angles about E (°): 5, 296.65; 6, 292.32 and 7 285.61) in
line with the expected increase in s-character of the lone
pair at E. The E–C bond lengths are similar to those
recorded for related monomeric complexes employing
sterically demanding ligands, e.g. [{2,6-(Ar0)2C6H3}-
O1
Ga1
C1
Cl2
Cl1
ꢀ
Fig. 1. Molecular structure of 2. Selected bond lengths (A) and angles
(°): Ga(1)–C(1) 1.978(7), Ga(1)–O(1) 1.940(5), Ga(1)–Cl(1) 2.1994(19),
Ga(1)–Cl(2) 2.1917(19), C(1)–Ga(1)–Cl(1) 116.0(2), C(1)–Ga(1)–Cl(2)
120.8(2), C(1)–Ga(1)–O(1) 111.8(2), Cl(1)–Ga(1)–Cl(2) 105.59(7),
Cl(1)–Ga(1)–O(1) 101.15(18), Cl(2)–Ga(1)–O(1) 98.56(18).
0
ꢀ
AsCl2] 2.005 A avge.; [{2,6-(Ar )2C6H3}SbCl2] 2.187(5)
in [{(Me3Si)3C}InCl2(l-Cl)Li(THF)3], but significantly
longer than in 3-coordinate complexes with trigonal
ꢀ
planar indium centres, e.g., 2.116(5) A in [(Mes*)InBr2]
ꢀ
ꢀ
A; [{2,6-(Mes)2C6H3}BiCl2] 2.267(5) A [16], though the
As–C distance in 5 is significantly shorter than that in
ꢀ
the analogous primary arsane [(tript)AsH2] 2.170(18) A
[9]. It is noteworthy that 7 is only the second structurally
[14]. Not surprisingly, the bridging In–Br bonds are
markedly longer than the terminal In–Br bond.
Br1
Br2
In1
O2
C8
C2
C1
Li1
Br3
C14
O1
ꢀ
Fig. 2. Molecular structure of 3. Selected bond lengths (A) and angles (°): In(1)–C(1) 2.176(6), In(1)–Br(1) 2.5090(9), In(1)–Br(2) 2.5706(9),
In(1)–Br(3) 2.5644(9), Li(1)–Br(2) 2.628(15), Li(1)–Br(3) 2.705(17), Li(1)–O(1) 1.897(16), Li(1)–O(2) 1.889(18), C(1)–In(1)–Br(1) 118.29(16), C(1)–
In(1)–Br(2) 115.41(17), C(1)–In(1)–Br(3) 114.87(16), Br(1)–In(1)–Br(2) 102.96(3), Br(1)–In(1)–Br(3) 105.55(3), Br(2)–In(1)–Br(3) 97.02(3), In(1)–
Br(2)–Li(1) 86.0(4), In(1)–Br(3)–Li(1) 84.5(3), O(1)–Li(1)–O(2) 114.0(9), O(1)–Li(1)–Br(2) 111.7(7), O(1)–Li(1)–Br(3) 113.3(8), O(2)–Li(1)–Br(2)
115.4(7), O(2)–Li(1)–Br(3) 108.2(6), Br(2)–Li(1)–Br(3) 92.3(5).

784
R.J. Baker et al. / Journal of Organometallic Chemistry 689 (2004) 781–790
ꢀ
Fig. 3. Molecular structure of 5. Selected bond lengths (A) and angles (°): As(1)–C(1) 1.980(3), As(1)–Cl(1) 2.1932(10), As(1)–Cl(2) 2.1945(9), C(1)–
As(1)–Cl(1) 98.77(9), C(1)–As(1)–Cl(2) 98.04(9), Cl(1)–As(1)–Cl(2) 99.84(4).
C11
C10
C12
9
C
C5
C4
C3
3
C1
C8
C6
C7
Cl1
C2
C20
C1
C15
1
Sb
C14
C19
C16
Cl2
C17
C18
ꢀ
Fig. 4. Molecular structure of 6. Selected bond lengths (A) and angles (°): Sb(1)–C(1) 2.226(8), Sb(1)–Cl(1) 2.368(2), Sb(1)–Cl(2) 2.363(2), C(1)–
Sb(1)–Cl(1) 99.1(2), C(1)–Sb(1)–Cl(2) 97.1(2), Cl(1)–Sb(1)–Cl(2) 96.12(8).

R.J. Baker et al. / Journal of Organometallic Chemistry 689 (2004) 781–790
785
C6
C5
C7
C4
Cl1
Cl2
C2
C3
C1
Bi1
C20
C8
C9
C15
C13
C14
C19
C16
10
C
C12
1
C1
C17
C18
ꢀ
Fig. 5. Molecular structure of 7. Selected bond lengths (A) and angles (°): Bi(1)–C(1) 2.299(11), Bi(1)–Cl(1) 2.523(3), Bi(1)–Cl(2) 2.468(3), C(1)–Bi(1)–
Cl(1) 96.6(3), C(1)–Bi(1)–Cl(2) 91.0(3), Cl(1)–Bi(1)–Cl(2) 98.01(10).
characterised example of a monomeric, uncoordinated
alkyl or aryl bismuth dihalide complex, the other being
[{2,6-(Mes)2C6H3}BiCl2].
a broad Sb–H stretching absorption at 1865 cmꢀ1
,
1
whilst its H NMR spectrum displays a resonance at d
3.16 ppm which was assigned to its hydride ligands.
These data are consistent with those for related primary
stibanes, e.g. [{(Me3Si)2HC}SbH2] [18] and [{2,6-
(Ar0)2C6H3}SbH2] [19] which show Sb–H stretches at
1860 and 1875 cmꢀ1 in their infrared spectra and hy-
dride resonances at d 2.12 and 2.66 ppm in their 1H
NMR spectra. Finally, comment should be made about
the high thermal stability of 9 (dec. 170 °C) which pre-
sumably arises from the kinetic protection afforded by
the 9-triptycenyl ligand and is comparable to the sta-
bility of the bulky terphenyl substituted stibane [{2,6-
(Ar0)2C6H3}SbH2] (dec. 195 °C).
The X-ray crystal structure of 8 was obtained and
found to be isomorphous to that recently described.
Therefore, details of this structure will not be included
here. Crystals of 9 suitable for X-ray diffraction were
obtained from diethyl ether. Its molecular structure
(Fig. 6) shows it to be monomeric, as is the case for
the only other structurally characterised uncoordi-
nated primary stibane, [{2,6-(Ar0)2C6H3}SbH2] [19].
Unfortunately, its hydride ligands could not be lo-
cated from difference maps but the Sb–C bond length
2.3. Triptycenyl group 15 hydride complexes
The primary pnictanes, [(tript)EH2], E ¼ P or As 8,
have previously been synthesised using a one-pot pro-
cedure involving the reaction of 9-lithiotriptycene with
either PCl3 or AsCl3 followed by in situ reduction with
LiAlH4 [8,9]. In the latter case the arsane could only be
isolated in an 11% yield. Moreover, attempts to extend
this methodology to the synthesis of the primary sti-
bane, [(tript)SbH2] 9, failed. Independently, we have
examined the reactions of the isolated and recrystallised
halide complexes, 5 and 6, with LiAlH4 in diethyl ether
which lead smoothly to the primary pnictanes, 8 and 9,
in good yields (67% and 65%, respectively). Unfortu-
nately, the related reaction of 7 with LiAlH4 did not lead
to the bismuthane, [(tript)BiH2], but to decomposition
and the deposition of elemental bismuth. This is not
surprising as to date there are no known thermally sta-
ble primary bismuthanes and only one structurally
characterised secondary bismuthane, [{2,6-(Mes)2-
C6H3}2BiH] [17].
ꢀ
of 2.206(6) A is not significantly different (within 3
The spectroscopic data for 8 are identical to those in
the previous report. The infrared spectrum of 9 exhibits
e.s.ds) to those in both 6 and [{2,6-(Ar0)2C6H3}SbH2]
ꢀ
(2.17 A avg.).

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R.J. Baker et al. / Journal of Organometallic Chemistry 689 (2004) 781–790
C11
C12
C9
C5
C6
C10
C13
C4
C8
C7
C3
C2
C20
C1
Sb1
C15
C14
C19
C16
C18
C
17
ꢀ
Fig. 6. Molecular structure of 9. Selected bond lengths (A): Sb(1)–C(1) 2.206(6), Sb(1)–C(1)–C(14) 111.9(4), Sb(1)–C(1)–C(8) 116.2(4), Sb(1)–C(1)–
C(2) 112.8(4).
3. Conclusion
DXP400 spectrometer operating at 400.13 and 100
MHz, respectively, or a Jeol Eclipse 300 spectrometer
operating at 300.52 and 75.57 MHz, respectively, and
The preparations of a range of thermally stable group
13 and 15 halide complexes incorporating the sterically
demanding 9-triptycenyl ligand have been discussed.
The arsenic and antimony halide complexes, 5 and 6,
have been used as precursors for the high yield syntheses
of their analogous primary pnictanes, 8 and 9. We are
currently examining the use of the triptycenyl group 13
halide complexes as precursors to group 13 diyls,
[(tript)MI:], via their reduction. In addition, the use of
the primary pnictanes as precursors to transition metal
terminal pnictinidene complexes, [LnM ¼ E(tript)], is
being examined and will be reported on in future
publications.
1
were referenced to the residual H or 13C resonances of
the solvent used. The numbering scheme for NMR as-
signments (Fig. 7) is based on IUPAC guidelines [20].
Mass spectra were recorded using a VG Fisons Platform
II instrument under APCI conditions, or obtained from
the EPSRC National Mass Spectrometric Service at
Swansea University (ESI). IR spectra were recorded
4. Experimental
All manipulations were carried out using standard
Schlenk and glove box techniques under an atmosphere
of high purity argon. Toluene, DME and THF were
distilled over potassium. Diethyl ether and hexane were
distilled over Na/K, whilst CH2Cl2 was distilled over
1
CaH2 then freeze/thaw degassed prior to use. H and
13C NMR spectra were recorded on either a Bruker
Fig. 7. Numbering scheme for NMR assignments.

R.J. Baker et al. / Journal of Organometallic Chemistry 689 (2004) 781–790
787
using a Nicolet 510 FT-IR spectrometer as a Nujol
4.3. [(tript)InBr(l-Br)2Li(OEt2)2] (3)
mulls between NaCl plates. Melting points were deter-
mined in sealed glass capillaries under argon and are
uncorrected. 9-Bromotriptycene [21] and 9-lithiotripty-
cene [8] were prepared by modifications of the literature
procedures. All other starting materials were obtained
commercially. PCl3 and AsCl3 were distilled immedi-
ately prior to use, whilst AlCl3, GaCl3 and InBr3 were
sublimed prior use. LiAlH4 was recrystallised from
Et2O.
To a solution of InBr3 (0.68 g, 1.91 mmol) in Et2O
(10 cm3) at )78 °C was added a solution of Li(tript)
(0.50 g, 1.92 mmol) in toluene (10 cm3) over 5 min. The
solution was allowed to warm to room temperature and
stirred for 12 h whereupon volatiles were removed in
vacuo and the resultant white residue extracted with
CH2Cl2 (10 cm3). Hexane was added to the extract until
the onset of crystallisation. Placement at )30 °C for 20 h
yielded 3 as colourless crystals (0.40 g, 28%); m.p. 102–
1
104 °C (dec); H NMR (400 MHz, CD2Cl2, 300 K): d
4.1. [(tript)AlCl2(OEt2)] (1)
3
1.27 (t, 12H, JHH ¼ 7:1 Hz, CH3), 3.77 (q, 8H,
3JHH ¼ 7:1 Hz, OCH2), 5.47 (s, 1H, C10H), 7.41 (m, 6H,
Ar–CH), 7.87 (m, 6H, Ar–CH); 13C NMR (75.5 MHz,
CD2Cl2, 300 K): d 14.6 (CH3), 53.8 (C10), 66.1 (OCH2),
124.8 (C2, C7, C14), 125.0 (C4, C5, C16), 125.4 (C3, C6,
C15), 125.7 (C1, C8, C13), 147.2 (C9a, C8a, C12), 147.8
(C4a, C5a, C11); IR(Nujol, cmꢀ1): m 1457(s), 1277(m),
1260(s), 1192(w), 1152(w), 1091(s), 1019(br), 800(s); MS
APCI: m=z (%) 528 [Mþ ) LiBr(OEt2)2, 15], 448 [trip-
tInBrþ, 100], 254 [triptHþ, 40].
To a solution of AlCl3 (0.15 g, 0.15 mmol) in Et2O
(10 cm3) held at )78 °C was added a solution of Li(tript)
(0.30 g, 0.15 mmol) in toluene (10 cm3) over 5 min. The
resultant solution was allowed to warm to room tem-
perature and stirred for 12 h whereupon volatiles were
removed in vacuo. The white residue was extracted with
CH2Cl2 (10 cm3) and hexane added to the onset of
crystallisation. Placement at )30 °C for 18 h yielded 1 as
a white powder (0.30 g, 63%); m.p. 218–221 °C (dec.);
1H NMR (300 MHz, CD2Cl2, 300 K): d 1.39 (t, 6H,
3
3JHH ¼ 7:1 Hz, CH3), 4.09 (q, 4H, JHH ¼ 7:1 Hz,
4.4. [(tript)PCl2] (4)
OCH2), 5.55 (s, 1 H, C10H), 7.08 (m, 6H, Ar–CH), 7.51
(m, 6H, Ar–CH); 13C NMR (75.5 MHz, CD2Cl2, 300
K): d 14.0 (CH3), 54.0 (C10), 69.6 (OCH2), 119.1 (C2,
C7, C14), 123.4 (C4, C5, C16), 123.7 (C3, C6, C15),
125.3 (C1, C8, C13), 143.9 (C9a, C8a, C12), 145.9 (C4a,
C5a, C11); IR(Nujol, cmꢀ1): m 1455(s), 1376(s), 1260(s),
1095(s), 801(s), 742(m); MS APCI: m=z (%) 351
[M ) OEtþ2 , 10], 254 [triptHþ, 100].
TriptBr (1.00 g, 3.00 mmol) in THF (30 cm3) was
cooled to )78 °C and BunLi (2.00 cm3 of a 1.6M solu-
tion in hexane, 3.20 mmol) added over 5 min. The re-
sultant suspension was warmed to room temperature
and stirred for 1 h. The suspension was then cooled to
)78 °C and PCl3 (0.40 cm3, 4.5 mmol) added dropwise
over 5 min. Warming to room temperature gave an or-
ange solution which was subsequently heated at reflux
for 90 min. Volatiles were then removed in vacuo and
the residue extracted into toluene (30 cm3). The extract
was filtered, concentrated to ca. 10 cm3 placed at )30 °C
for 15 h to yield 4 as an off-white microcrystalline
4.2. [(tript)GaCl2(THF)] (2)
To a solution of GaCl3 (0.32 g, 1.81 mmol) in THF
(10 cm3) held at )78 °C was added a solution of Li(tript)
(0.50 g, 1.92 mmol) in toluene (10 cm3) over 5 min. The
resultant solution was warmed to room temperature and
stirred for 12 h. Volatiles were then removed in vacuo
and the white residue extracted with CH2Cl2 (10 cm3).
Hexane was added to the solution until the onset of
crystallisation. Placement at )30 °C for 12 h yielded 2 as
colourless crystals (0.83 g, 96%); m.p. 238–242 °C (dec.);
1H NMR (300 MHz, CD2Cl2, 300 K): d 2.09 (m, 4H,
CH2), 4.39 (m, 4H, OCH2), 5.55 (s, 1 H, C10H), 7.42 (m,
6H, Ar–CH), 7.62 (m, 6H, Ar–CH); 13C NMR (75.5
MHz, CD2Cl2, 300 K): d 25.2 (CH2), 57.1 (C10), 73.6
(OCH2), 124.1 (C2, C7, C14), 125.1 (C4, C5, C16), 125.9
(C3, C6, C15), 128.6 (C1, C8, C13), 146.4 (C9a, C8a,
C12), 147.4 (C4a, C5a, C11); IR(Nujol, cmꢀ1): m 1453(s),
1377(s), 1342(s), 1262(m), 1197(m), 1132(w), 1112(m),
1076(m), 838(s); MS EI: m=z (%) 393 [M ) THFþ, 20],
254 [triptHþ, 100]; Accurate Mass MS (EI) Calc. for
Mþ ) THF: C20H13Cl2Ga: 391.9645. Found 391.9636.
1
powder (0.67 g, 63%); m.p. 222–227 C; H NMR (300
MHz, C6D6, 298 K) d 5.02 (s, 1H, C10H), 6.67–7.76 (m,
12H, Ar–CH); 13C NMR (75.6 MHz, C6D6, 298 K) d
1
54.6 (C10), 59.3 (d, JPC ¼ 63:4 Hz, C9), 124.8 (d,
4JPC ¼ 2:3 Hz, C2, C7, C14), 123.9 (C4, C5, C16), 125.7
3
(C3, C6, C15), 126.1 (d, JPC ¼ 4:6 Hz, C1, C8, C13),
2
142.9 (d, JPC ¼ 17:3 Hz, C9a, C8a, C12), 147.7 (d,
3JPC ¼ 5:8 Hz, C4a, C5a, C11); 31P NMR (121.7 MHz,
C6D6, 298 K) d 182.1 (s); IR(Nujol) m/cmꢀ1 1287(m),
1257(m), 1197(m), 1132(m), 1036(m), 730(s); MS EI:
m=z (%) 355 [Mþ, 35], 253 [triptþ, 100]; Accurate mass
MS (EI) Calc. for C20H13PCl2: 354.0126. Found:
354.0128.
4.5. [(tript)AsCl2] (5)
TriptBr (1.00 g, 3.00 mmol) in THF (30 cm3) was
cooled to )78 °C and BunLi (2.00 cm3 of a 1.6 M

788
R.J. Baker et al. / Journal of Organometallic Chemistry 689 (2004) 781–790
solution in hexane, 3.20 mmol) added over 5 min. The
resultant suspension was warmed to room temperature
and stirred for 1 h. It was then cooled to )78 °C and
AsCl3 (0.40 cm3, 4.5 mmol) added dropwise over 5 min.
Warming to room temperature gave an orange solution
which was subsequently heated at reflux for 90 min.
Volatiles were removed in vacuo and the residue ex-
tracted into toluene (30 cm3). Concentration and
placement at )30 °C overnight gave colorless crystals of
point of crystallisation and the solution placed at )30 °C
for 15 h to give colourless crystals of 7 (0.20 g, 13%);
m.p. 155 °C, 1H NMR (300.5 MHz, C6D6, 298 K) d 5.10
(s, 1H, C10-H), 6.60–7.30 (m, 12H, Ar–H), 13C NMR
(75.6 MHz, C6D6, 298 K) d 53.3 (C10), 53.2 (C9), 122.5
(C2, C7, C14), 124.0 (C4, C5, C16), 124.9 (C3, C6, C15),
127.9 (C1, C8, C13), 144.4 (C9a, C8a, C12), 146.9 (C4a,
C5a, C11); IR(Nujol) m/cmꢀ1
: 1296(m), 1255(m),
1187(m), 1137(m), 475(m, Bi–Cl); MS CI m=z (%): 533
[Mþ, 15], 253 [tripþ, 100]; Accurate mass MS (CI) Calc.
mass for C20H13Bi35Cl2: 532.0193. Found: 532.0188.
1
5 (0.70 g, 58%); m.p. 198–200 °C, H NMR (400 MHz,
CD2Cl2, 300 K): d 5.40 (s, 1H, C10H), 6.99–7.39 (m,
12H, Ar–H); 13C NMR (75.5 MHz, CD2Cl2, 300 K): d
54.1 (C10), 54.4 (C9), 124.3 (C2, C7, C14), 125.2 (C4,
C5, C16), 125.7 (C3, C6, C15), 126.0 (C1, C8, C13),
145.3 (C9a, C8a, C12), 147.3 (C4a, C5a, C11); IR(Nu-
jol) m/cmꢀ1: 1285(m), 1262(m), 1189(m), 1132(m), 730(s),
479 (m, As–Cl); MS APCI m=z (%): 309 [Mþ, 100].
4.8. [(tript)AsH2] (8)
A suspension of (tript)AsCl2 (0.65 g, 1.6 mmol) in
diethyl ether (20 cm3) was added to a solution of LiAlH4
(0.08 g, 2.00 mmol) in diethyl ether (20 cm3) at )78 °C
over 5 min. The resultant suspension was warmed to
room temperature and stirred in the absence of light for
60 h. The solution was filtered, concentrated to ca. 20
cm3 at placed at )30 °C overnight to give colourless
crystals of 8 (0.36 g, 67%). The spectroscopic data were
found to be consistent with those previously reported
for this compound [9].
4.6. [(tript)SbCl2] (6)
TriptBr (1.00 g, 3.00 mmol) in THF (30 cm3) was
cooled to )78 °C and BunLi (2.00 cm3 of a 1.6 M so-
lution in hexane, 3.20 mmol) added. The resultant sus-
pension was warmed to room temperature and stirred
for 1 h. The suspension was then cooled to )78 °C and a
solution of SbCl3 (1.03 g, 4.5 mmol) in THF (10 cm3)
added dropwise over 10 min. Warming the mixture to
room temperature afforded an orange solution which
was heated at reflux for 30 min. Volatiles were removed
in vacuo and the residue extracted into toluene (30 cm3).
Hexane was added to the extract to the point of crys-
tallisation and the solution was placed at )30 °C for 15
h to give colourless crystals of 6 (0.70 g, 52%); m.p. 246–
4.9. [(tript)SbH2] (9)
A suspension of (tript)SbCl2 (0.50 g, 1.1 mmol) in
diethyl ether (20 cm3) was added to a solution of LiAlH4
(0.08 g, 2.00 mmol) in diethyl ether (20 cm3) at )78 °C
over 5 min. The resultant suspension was warmed to
room temperature and stirred in the absence of light for
60 h. The solution was then filtered, concentrated to ca.
20 cm3 and placed at )30 °C overnight to give colourless
1
247 °C, H NMR (300.5 MHz, C6D6, 298 K) d 5.41 (s,
1
crystals of 9 (0.36 g, 67%); m.p. 170–172 °C dec., H
1H, C10H), 7.03–7.54 (m, 12H, Ar–H); 13C NMR (75.5
MHz, CD2Cl2, 300 K): d 54.3 (C10), 54.4 (C9), 122.5
(C2, C7, C14), 124.9 (C4, C5, C16), 126.1 (C3, C6, C15),
126.4 (C1, C8, C13), 145.4 (C9a, C8a, C12), 147.9 (C4a,
NMR (300.5 MHz, C6D6, 298 K) d 3.16 (s, 2H, SbH2),
5.16 (s, 1H, C10-H), 6.82–6.75 (m, 6H, ArH), 7.20–7.49
(m, 6H, ArH); 13C NMR (75.6 MHz, C6D6, 298 K) d
54.9 (C10), 55.1 (C9), 123.5 (C2, C7, C14), 124.9 (C4,
C5, C16), 125.1 (C3, C6, C15), 126.1 (C1, C8, C13),
146.6 (C9a, C8a, C12), 148.7 (C4a, C5a, C11); IR(Nu-
jol): m/cmꢀ1 1865(m, Sb–H); MS CI m=z (%): 377 [Mþ,
20], 253 [tripþ, 100]; Accurate mass MS (CI) Calc. mass
for C20H11521Sb2: 376.0106, measured mass: 376.0200.
C5a, C11); IR(Nujol) m/cmꢀ1
: 1289(m), 1259(m),
1189(m), 1137(m), 545(m), 465(m, Sb–Cl); MS APCI
m=z (%): 445 [Mþ, 100]; Accurate mass MS (CI) Calc.
mass for C20H11321SbCl2: 444.9505. Found: 444.9518.
4.7. [(tript)BiCl2] (7)
4.10. Crystallographic studies
TriptBr (1.00 g, 3.00 mmol) in THF (30 cm3) was
cooled to )78 °C and BunLi (2.00 cm3 of a 1.6 M so-
lution in hexane, 3.20 mmol) added. The resultant sus-
pension was warmed to room temperature and stirred
for 1 h. It was then cooled to )78 °C and a solution of
BiCl3 (1.42 g, 4.5 mmol) in THF (10 cm3) added drop-
wise over 5 min. The suspension was warmed to room
temperature and stirred for 16 h in the absence of light.
Volatiles were removed in vacuo and the residue ex-
tracted into toluene (30 cm3). Hexane was added to the
Crystals of 2, 3, 5, 6, 7 and 9 suitable for X-ray
structural determination were mounted in silicone oil.
Crystallographic measurements were made using a No-
nius Kappa-CCD diffractometer. The structures were
solved by direct methods and refined on F 2 by full-
matrix least-squares (SHELX 97) [22] using all unique
data. All non-hydrogen atoms are anisotropic with H-
atoms included in calculated positions (riding model).
The hydrogens attached to Sb(1) in the structure of 9

R.J. Baker et al. / Journal of Organometallic Chemistry 689 (2004) 781–790
789
Table 1
Summary of crystallographic data for complexes 2 ꢁ (CH2Cl2)0:5, 3, 5 ꢁ (C7H8)0:5, 6, 7 ꢁ (C6H14
)
and 9
0:5
2 ꢁ (CH2Cl2)0:5
3
5 ꢁ (C7H8)0:5
6
7 ꢁ (C6H14
)
9
0:5
Chemical formula
Formula weight
C24:5H22Cl3GaO
508.49
150(2)
C28H33Br3InLiO2
763.03
150(2)
C23:5H17AsCl2
445.19
150(2)
C20H13Cl2Sb
445.95
150(2)
Monoclinic
Cc
C23H20BiCl2
576.27
150(2)
C20H15Sb
377.07
150(2)
T (K)
Crystal system
Space group
Monoclinic
P21=c
11.440(2)
14.819(3)
14.988(3)
90
Orthorhombic
P212121
10.565(6)
14.212(3)
20.028(4)
90
Monoclinic
C2=c
22.929(5)
10.922(2)
16.060(3)
90
Monoclinic
P21=n
13.272(3)
9.1190(18)
16.432(3)
90
Monoclinic
P21=n
11.975(2)
8.8310(18)
15.044(3)
90
ꢀ
a (A)
15.769(3)
11.103(2)
20.103(4)
90
ꢀ
b (A)
ꢀ
c (A)
a (°)
b (°)
c (°)
103.74(3)
90
90
90
107.11(3)
90
108.02(3)
90
96.65(3)
90
107.18(3)
90
3
ꢀ
V (A )
2468.2(9)
4
1.452
3007.2(10)
4
4.794
3843.9(13)
8
2.051
3347.1(12)
8
1.963
1975.3(7)
4
9.200
1519.9(5)
4
1.805
Z
l(Mo Ka) (mmꢀ1
)
Unique reflections
R1ðI > 2rðIÞÞ
4293
0.0724
0.2269
5832
0.0462
0.0838
3519
0.0371
0.0858
5256
0.0440
0.1044
3424
0.0505
0.1271
3477
0.0768
0.1591
wR02 (all data)
could not be located from difference maps and were
not refined. The asymmetric unit of 6 contains two
crystallographically independent molecules though no
significant geometric differences were found between
them. Therefore, the metric parameters for only one are
discussed in the text. Compounds 3 and 6 crystallise in
chiral space groups (P212121 and Cc, respectively) and
the absolute structures of each have been assigned based
on the values of the Flack parameters after final re-
finements (0.021(12) and 0.01(3), respectively). Crystal
data, details of data collections and refinement are given
in Table 1.
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