Bidentate amino- and iminophosphine ligands in mono- and dinuclear gold(I) complexes: Synthesis, structures and AuCl displacement by AuC6F5

Article abstract of DOI:10.1016/j.inoche.2007.01.022

Bidentate imino- and aminophosphine ligands were prepared by firstly a Schiff-base condensation reaction between 2-(diphenylphosphino)benzaldehyde and the corresponding primary amines to afford the imino derivatives and secondly reduction of the imines with NaBH₄ to the aminophosphine ligands in satisfactory yields. The ligands readily reacted with chlorogold(I) compounds to produce new mononuclear iminophosphine- and dinuclear aminophosphine chlorogold(I) complexes. Further, reaction of the dinuclear chlorogold complex with C₆F₅Au(tht) (tht = tetrahydrothiophene) led to the displacement of one AuCl moiety by AuC₆F₅ forming a digold(I) mixed halogen/organometallic complex. Both digold(I) complexes displayed intramolecular Au?Au interactions, whilst the di(chlorogold) complex also showed an intermolecular Au? Au interaction, as determined by X-ray crystallography. The displacement of only one of the two AuCl groups presumably relates to the strength of the Au-P bond (inert) vs. the weakness of the Au-N bond (labile), the latter being more easily broken.

Full text of DOI:10.1016/j.inoche.2007.01.022

Inorganic Chemistry Communications 10 (2007) 538–542
www.elsevier.com/locate/inoche
Bidentate amino- and iminophosphine ligands in mono- and
dinuclear gold(I) complexes: Synthesis, structures and
AuCl displacement by AuC6F5
*
D. Bradley G. Williams , Telisha Traut, Frederik H. Kriel, Werner E. van Zyl
Department of Chemistry, University of Johannesburg, P.O. Box 524, Auckland Park 2006, South Africa
Received 28 November 2006; accepted 27 January 2007
Available online 2 February 2007
Abstract
Bidentate imino- and aminophosphine ligands were prepared by firstly a Schiff-base condensation reaction between 2-(diph-
enylphosphino)benzaldehyde and the corresponding primary amines to afford the imino derivatives and secondly reduction of the imines
with NaBH4 to the aminophosphine ligands in satisfactory yields. The ligands readily reacted with chlorogold(I) compounds to produce
new mononuclear iminophosphine- and dinuclear aminophosphine chlorogold(I) complexes. Further, reaction of the dinuclear chloro-
gold complex with C6F5Au(tht) (tht = tetrahydrothiophene) led to the displacement of one AuCl moiety by AuC6F5 forming a digold(I)
mixed halogen/organometallic complex. Both digold(I) complexes displayed intramolecular AuÁ Á ÁAu interactions, whilst the di(chloro-
gold) complex also showed an intermolecular AuÁ Á Á Au interaction, as determined by X-ray crystallography. The displacement of only
one of the two AuCl groups presumably relates to the strength of the Au–P bond (inert) vs. the weakness of the Au–N bond (labile), the
latter being more easily broken.
ꢀ 2007 Elsevier B.V. All rights reserved.
Keywords: Mono- and dinuclear gold(I) complexes; P–N bidentate ligands; Iminophosphine; Aminophosphine; Pentafluorophenyl; X-ray crystal struc-
tures
There is a growing interest in the co-ordination chemis-
try of bi- and multidentate ligands containing both hard (N
donor) and soft (P donor) Lewis bases [1,2]. Such hemila-
bile ligand systems have the potential to bind soft metal
centers such as those of the platinum group metals (PGMs)
strongly via phosphorus and weakly via nitrogen, which
allows for the facile displacement of the chelating N-moi-
ety. This scenario is frequently desired in homogeneous
catalytic reactions [3]. The differing reactivity of chelating
P–N vs. P–P type ligands has previously been compared
[4] and, amongst the PGMs in particular, the catalytic
application of P–N-based ligands has been investigated
[5,6].
Complexes with bidentate hemilabile ligands show
potential not only in catalytic cycles, but also in medicinal
applications. For example, various studies of gold(I) have
been related to anti-arthritic [7,8], anti-tumour [7,9] and
anti-microbial physiological activities [10,11]. Although
gold(I) mono- and bisphosphine compounds have been
extensively studied [12] together with their mechanisms of
cytotoxity and anti-tumour activity [13], bidentate gold(I)
compounds that utilise both a hard and soft donor atom
are only poorly represented in the literature [14]. Among
the ‘hard’ donor type atoms, the co-ordination chemistry
of gold(I) oxygen compounds [15,16] shows a distinct pau-
city in the literature, while gold(I) complexes with nitrogen
donor functions are more common yet less stable than their
phosphine analogues [17,18].
*
We herein report the preparation and characterisation
of the three new complexes of gold(I) with bidentate P–N
Corresponding author. Tel.: +27 11 489 3431; fax: +27 11 489 2819.
E-mail address: bwilliams@uj.ac.za (DBG Williams).
1387-7003/$ - see front matter ꢀ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2007.01.022

DBG Williams et al. / Inorganic Chemistry Communications 10 (2007) 538–542
539
ligands where, depending its nature, the ligand binds to
P h2
P
Au(I) either in a mono- or bidentate fashion to form the
corresponding Au(I) complexes. Additionally, we report
the facile displacement of an N-bound AuCl moiety by
an organometallic AuC6F5 group.
ClAu(tht)
1b
Au
Cl
The Schiff-base iminophosphine ligands 1a and 1b were
prepared using a condensation reaction by treatment of 2-
(diphenylphosphino)benzaldehyde with the corresponding
primary amines in toluene under reflux and were isolated
in high yields (>90%) by vacuum distillation (0.05 mm Hg,
250 ꢁC). Reduction of ligands 1a and 1b with NaBH4 in dry
MeOH formed analogous amines 2a and 2b in satisfactory
yields (>70%) after bulb-to-bulb vacuum distillation
(0.05 mm Hg, 250 ꢁC). (See Scheme 1).
Complex 3 was prepared [19] by the reaction of imino-
phosphine ligand 1a with one or two molar equivalents
of ClAu(tht) (tht = tetrahydrothiophene), respectively
(Scheme 2). In the case where one equivalent of gold(I)
was used, the gold complex was obtained in good yield
(73%) in CHCl3 as solvent. However, when two equivalents
of the ClAu(tht) were added to the ligand, with the inten-
tion of probing the possibility of binding two gold atoms
through the P and N atoms, respectively, no dinuclear gold
complexes were observed. Instead, autocatalytic decompo-
sition and subsequent reduction of Au(I) to colloidal gold
was observed by the presence of an insoluble purple col-
oured precipitate.
N
H
But
3
Scheme 2. Preparation of mononuclear gold complex 3.
Ph
Ph
P
Au
2 Cl Au(tht)
Cl
2a
Cl Au
N
H
Pri
C 6 F5 Au(tht)
4
Ph
Ph
P
Au
C6 F5
Au
Cl
N
H5
i
Pr
In contrast, when aminophosphine ligand 2a was
reacted with one molar equivalent of ClAu(tht), the reac-
tion proceeded cleanly to produce dinuclear gold(I) com-
plex 4 [20] in 32% yield (Scheme 3). Improvement in the
yield to 67% (based on the ligand as a limiting reagent)
could be obtained by performing the same reaction using
two molar equivalents of the Au(I) reagent. Some decom-
position of the Au(I) reagent to Au(0) was also observed
in this instance. The formation of both 3 and 4 was com-
plete within 30 minutes as determined by 13P NMR spec-
troscopy. Here, the free ligands 1b and 2a manifested
Scheme 3. Preparation of dinuclear gold complexes 4 and 5.
singlet resonances at À11.9 ppm and À15.7 ppm, respec-
tively. Upon complexation, a significant downfield shift
of these signals from 31.0 to 26.0 ppm for 3 and 4, respec-
tively, was observed with concomitant disappearance of the
signal of the original free ligand, providing a diagnostic
analytical tool by which the complexation process could
be followed. In these complexes, the methylene moiety car-
ries two diastereotopic protons (arising from the N-centred
chirality induced by Au-complexation). This diastereotop-
icity is not observed in the NMR spectra of the com-
pounds, possibly due to rapid flexing of the large (by
virtue of the two Au atoms contained therein and the rela-
tively long Au–Au bond) seven-membered ring which may
preclude a preferred conformation being observable on the
NMR time-scale, leading to an averaging of the methylene
proton signals to form the observed singlet.
Complex 5 was prepared in a small-scale reaction
(Scheme 3) by reaction of chlorogold complex 4 with one
molar equivalent of C6F5 Au(tht). The reaction led to the
selective displacement of the N-bound AuCl fragment in
4 by AuC6F5, leaving the already P-bound AuCl moiety
intact. To the best of our knowledge, this is the first exam-
ple of an AuCl fragment being substituted (through N–Au
bond cleavage) by an organogold(I) fragment. Since only
one of the two AuCl fragments was substituted, the relative
P–Au(I) and N–Au(I) bond strengths are contrasted, par-
ticularly with regard to the displacement by organometallic
t
iPrNH2 or BuNH2
Ph2 P
Ph2 P
Ph CH3 , reflux
N
O
R
H
H
1a: R= iPr
t
NaBH 4
MeOH
1b: R= Bu
Ph2 P
H
N
R
2a : R = Pr
2b : R = tBu
H
H
i
Scheme 1. Ligand synthesis.

540
DBG Williams et al. / Inorganic Chemistry Communications 10 (2007) 538–542
moieties. Displacement of the remaining chlorine atom
may be possible through the treatment with LiC6F5, which
is known [21] to react with chlorogold(I), potentially pro-
viding a step-wise synthesis of a bis-organogold(I) com-
pound through selective cleavage of Au–N and Au–Cl
bonds.
Single crystals of complexes 3–5 were grown from solu-
tion [19,20] and were subjected to X-ray crystallographic
analysis [22]. The structure of complex 3 is shown in
Fig. 1. The data for 3 did not refine well [22] and the struc-
ture is reported primarily for its molecular structure and its
comparison with other structures shown: bond lengths and
angles for this structure are not used for comparison pur-
poses due to the poor refinement. Nevertheless, no unusual
bond angles or distances were observed and the complex
showed a virtually linear P–Au–Cl system (bond angle of
177ꢁ) as is normally anticipated for two-coordinate Au(I)
compounds.
Compared with complex 3, the most important feature
demonstrated by the crystal structures of complexes 4
(Figs. 2 and 3) and 5 (Fig. 4) is that each shows the pres-
ence of dinuclear gold(I) centers with Au–Au interactions.
The solid state structure of complex 4 is particularly inter-
esting and unusual in that it shows the presence of intramo-
˚
˚
lecular (2.98 A) as well as intermolecular (3.19 A) AuÁ Á ÁAu
interactions (Fig. 3). The intramolecular AuÁ Á ÁAu distance
˚
˚
is significantly shorter in 4 than it is in 5 (2.98 A vs. 3.10 A),
presumably as a consequence of the more sterically encum-
bered aromatic ring in 5 together with electronic factors. In
complex 4, the P–Au–Cl angle (175.26ꢁ) is bent slightly fur-
ther from linearity than that of the lighter N–Au–Cl conge-
ner at 177.36ꢁ. The crystallography also confirmed the
reduction of the imine (shorter imine C@N bond (C37–
˚
N1) of 1.25 A in 3) to the amine (C–N bond distance
˚
(C37–N1) of 1.50 A in 4).
Fig. 3. Portion of the crystal packing for complex 4, showing intra- and
intermolecular gold–gold interactions.
Fig. 1. ORTEP structure of 3 with 50% probability ellipsoids.
Fig. 2. ORTEP diagram 4 with 50% probability ellipsoids. Selected
˚
interatomic distances (A) and angles (ꢁ): C37–N1 1.504(8), C38–C39B
1.479(12), C38–N1 1.507(9), C38–C39A 1.531(11), N1–Au2 2.087(6), Cl1–
Au1 2.2916(19), Cl2–Au2 2.2721(18), P1–Au1 2.2380(18), Au1–Au2
2.9821(5)
(intra),
Au2–Au2
3.1998(6)
(inter);
N1–C37–C36
110.3(5),C39B–C38–N1 113.0(7), C39B–C38–C39A 111.4(7), N1–C38–
C39A 108.2(6),C37–N1–C38 113.4(5), C37–N1–Au2 110.5(4), C38–N1–
Au2 114.6(4), P1–Au1–Cl1 175.26(6), P1–Au1–Au2 91.87(4), N1–Au2–
Cl2 177.36(15), Cl1–Au1–Au2 92.28(4). (Note: The N-centre is an NH
group, not an amide.)
Fig. 4. ORTEP structure of 5 with 50% probability ellipsoids. Selected
˚
interatomic distances (A) and angles (ꢁ): N1–Au2 2.110(8), P1–Au1
2.244(2), Cl1–Au1 2.315(2), Au1–Au2 3.1013(10), P1–Au1–Cl1 169.68(8),
P1–Au1–Au2 96.39(6). (Note: The N-centre is an NH group, not an
amide.)

DBG Williams et al. / Inorganic Chemistry Communications 10 (2007) 538–542
541
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The solid state structure of the di-gold(I) mixed halogen/
organometallic complex 5 is shown in Fig. 4. The P–Au–Cl
angle in 5 (169.68ꢁ) is significantly more bent than between
the same three atoms in complex 4 (175.26ꢁ). This may rea-
sonably be attributed to a steric bulk introduced to the sys-
tem by the additional Au-bound aromatic ring in 5.
In conclusion, we have demonstrated that P–N biden-
tate ligands may bind to either one or two Au(I) ions,
depending on the system in question. The Au atoms in
dinuclear complexes manifested intramolecular Au–Au
interactions, as well as intermolecular Au–Au interactions
in one instance. We have further shown a rare if not unique
Au–Au exchange reaction for this system, replacing inor-
ganic gold(I) for an organogold analogue.
(c) J.D.E.T. Wilton-Ely, H. Ehlich, A. Schier, H. Schmidbaur, Helv.
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Biochemistry and Technology, John Wiley and Sons, Chichester,
1999, p. 311;
(b) H. Schmidbaur, A. Kolb, P. Bissinger, Inorg. Chem. 31 (1992) 4370;
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1. Supplementary material
[19] Synthesis of 3: To a stirred solution of 1b (0.100 g, 0.290 mmol) in
diethyl ether (20 mL) was added 1 M equivalent of ClAu(tht) (0.093 g,
0.290 mmol) dissolved in chloroform (5 mL). The mixture was stirred
at room temperature for 5 min during which time a precipitate
formed. The solvent was decanted and the precipitate washed with
diethyl ether (5 · 5 mL) and hexane (3 · 5 mL) and dried in vacuo.
Yield (0.125 g, 0.216 mmol) 74%. M.p. 192–194 ꢁC (white powder),
208–210 ꢁC (crystals from layered CHCl3/hexane). 1H NMR
(300 MHz, CDCl3): dH 8.67 (d, 1H, J = 1.8 Hz, imine-H), 7.86
(ddd, 1H, J = 7.6, 4.4 and 1.4 Hz, aromatic), 7.61–7.38 (m, 11H,
aromatic), 7.31 (tt, 1H, J = 7.7 and 1.7 Hz, aromatic), 6.77 (ddd, 1H,
J = 13.2, 7.8 and 1.2 Hz, aromatic), 0.99 (s, 9H, C(CH3)3). 13C NMR
(75 MHz, CDCl3)dC 153.7 (d, 1C, J = 6.5 Hz, imine-C), 139.3 (d, 1C,
J = 7.1 Hz, C1), 134.3 (d, 4 C, J = 12.7 Hz, ortho-C phenyl), 134.1 (d,
1C, J = 7.1 Hz), 131.7 (d, 1C, J = 2.6 Hz, C5), 131.5 (d, 2C,
J = 2.6 Hz, para-C phenyl), 131.2 (d, 1C, J = 8.6 Hz), 130.0 (d, 2C,
J = 63.2 Hz, ipso-C phenyl), 129.7 (d, 1C, J = 10.5 Hz), 129.0 (d, 4C,
J = 12.0 Hz, meta-C phenyl), 127.2 (d, 1C, J = 55.1 Hz, C2), 58.6 (s,
1C, C(CH3)3), 29.6 (s, 3C, C(CH3)3). 31P NMR (121 MHz, CDCl3) dP
31.0 (s, 1P). FAB-MS: m/z 577 [M + 1]+.
CCDC 624478, 624479 and 624480 contain the
supplementary crystallographic data for this paper. These
data can be obtained free of charge via http://www.ccdc.ca-
m.ac.uk/conts/retrieving.html, or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: +44 1223 336 033; or e-mail:
deposit@ccdc.cam.ac.uk.
Acknowledgement
The authors would like to thank Project AuTEK (Min-
tek and Harmony Gold) for permission to publish the re-
sults and financial support.
References
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otto, Organometallics 25 (2006) 1028.
[20] Preparation of 4: Similar to 3 but using 2 equivalents of ClAu(tht).
White powder. Yield: (0.160 g) 67% yield. M.p. 124–126 ꢁC (powder),
241–243 ꢁC (crystals from CHCl3/hexane). 1H NMR (300 MHz,
CDCl3) dH 7.65 (m, 1H, aromatic), 7.57–7.42 (m, 11H, aromatic), 7.20
(tt, 1H, J = 7.5 and 1.5 Hz, aromatic), 6.77 (ddd, 1H, J = 12.9, 7.8
and 1.2 Hz, aromatic), 4.09 (s, 2H, HNCH2R), 2.64 (pentet, 1H,
J = 6.2 Hz, CH(CH3)2), 1.30 (broad s, 1H, NH), 0.84 (d, 6H,
J = 6.3 Hz, CH(CH3)2). 13C NMR (75 MHz, CDCl3) dC 144.7 (d,
1C, J = 11.0 Hz, C1), 134.4 (d, 4C, J = 14.0 Hz, ortho-C phenyl),
133.4 (d, 1C, J = 8.0 Hz), 131.9 (d, 3C, J = 2.5 Hz, para-C phenyl,
C5), 130.8 (d, 1C, J = 9.0 Hz), 129.3 (d, 4C, J = 12.0 Hz, meta-C
phenyl), 129.0 (d, 2C, J = 62.6 Hz, ipso-C phenyl), 127.2 (d, 1C,
J = 10.0 Hz), 126.5 (d, 1C, J = 59.1 Hz, C2), 50.4 (d, 1C, J = 11.6 Hz,
HNCH2), 48.8 (s, 1C, CH(CH3)2), 22.7 (s, 2C, CH(CH3)2). 31P NMR
(121 MHz, CDCl3) dP 26.0 (s, 1P). FAB-MS: m/z 566 [M-AuCl]+.
Preparation of 5: To a stirred solution of C6F5Au(tht) (0.001 g,
0.0022 mmol) dissolved in dichloromethane (1 mL) was added in a
drop-wise manner one molar equivalent of 4 (0.00175 g, 0.0022 mmol)
dissolved in dichloromethane (0.5 mL). The mixture was stirred at
room temperature for 1 h after which the solvent was evaporated to
ca. 0.5 mL. Single crystals suitable for an X-ray analysis could be
obtained by the layering of the solution with hexane. Yield (0.00178 g,
0.00192 mmol) 87%. M.p. 168–170 ꢁC (crystals from DCM/hexane).
FAB-MS: m/z 894.3 [M-Cl]+.
[2] R.C.J. Atkinson, V.C. Gibson, N.J. Long, Chem. Soc. Rev. 33 (2004)
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[21] R. Uson, A. Laguna, M. Laguna, Inorg. Synth. 26 (1989) 85–91.
[22] The intensity data were collected at 173 K on a Bruker SMART 1 K
CCD diffractometer with area detector using graphite monochro-
[13] M.J. McKeage, L. Maharaj, S.J. Berners-Price, Coord. Chem. Rev.
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ani, Eur. J. Inorg. Chem. 10 (2005) 1955.
˚
mated Mo Ka radiation (k = 0.71073 A, 50 kV, 30 mA). Data

542
DBG Williams et al. / Inorganic Chemistry Communications 10 (2007) 538–542
reduction was carried out using the program SAINT+ [23] and face
data), R1 = 0.0889, wR2 = 0.2221, GOF = 1.015. Crystal data for
4:C22H24Au2Cl2NP 0.5(CHCl3); M = 857.91 g/mol, triclinic, space
indexed absorption corrections were made using the program XPREP
[23]. The structures were solved by direct methods using SHELXTL
[24]. Non-hydrogen atoms were first refined isotropically followed by
the anisotropic refinement by full matrix least-squares calculations
based on F2 using SHELXTL. Hydrogen atoms were first located in
the difference map then positioned geometrically and allowed to ride
on their respective parent atoms. Diagrams and publication material
were generated using SHELXTL and PLATON [25]. Complex 4
contains a disordered chloroform molecule. Its contribution to the
electron density map was accounted for using the PLATON
SQUEEZE algorithm. The contribution of the chloroform molecule
has been included in the molecular and chemical formulas as well as
F(000). Crystal data for 3:C23H24AuClNP; M = 577.82 g/mol,
˚
˚
group
P-1
(No.
2),
a = 8.1563(10) A,
b = 0.0935(13) A,
˚
c = 16.4581(18) A, a = 94.575(7)ꢁ, b = 93.152(7)ꢁ, c = 109.791(7)ꢁ,
V = 1266.0(3) A , Z = 2, l(Mo Ka) = 12.019 mmÀ1, F(000) = 798,
3
˚
16943 reflections measured, 6109 unique, R(int) = 0.084,
R1 = 0.0331, wR2 = 0.0988 (for all data), GOF = 1.087. Crystal data
for 5: C28H24Au2ClF5 NP; M = 929.84 g/mol, monoclinic, P21/n,
˚
˚
˚
a = 8.685(4) A,
b = 14.427(6) A,
c = 22.578(10) A,
a = 9À0ꢁ1,
3
˚
b = 92.900(8)ꢁ, c = 90ꢁ, V = 2825(2) A , Z = 4, Dc = 2.186 g cm
,
l(Mo Ka) = 10.576 mmÀ1, F(000) = 1736, 15880 reflections mea-
sured, 6823 unique, R(int) = 0.1067, R1 = 0.0702, wR2 = 0.1481 (all
data), GOF = 1.063.
[23] Bruker (1999). SAINT+. Version 6.02 (includes XPREP and SAD-
ABS). Bruker AXS Inc., Madison, Wisconsin, USA.
[24] Bruker (1999). SHELXTL. Version 5.1. (includes XS, XL, XP,
XSHELL) Bruker AXS Inc., Madison, Wisconsin, USA.
[25] A.L. Spek, J. Appl. Cryst. 36 (2003) 7.
˚
˚
monoclinic, space group P21/n, a = 11.0466(19) A, b = 15.638(3) A,
3
˚
˚
c = 12.6741(19) A, b = 93.709(7)ꢁ, V = 2184.9(6) A , Z = 4,
Dc = 1.757 g cmÀ1, l(Mo Ka) = 6.936 mmÀ1, F(000) = 1120, 11936
reflections collected, 5293 unique, R1 = 0.1180, wR2 = 0.2529 (for all