Synthesis, coordination chemistry, and metal complex reactivity of (dimethylamino)methyl-substituted triarylphosphanes; X-ray study on [AuCl(PPh3 - NArn)] (Ar = 1-C6H 3(CH2NMe2)2

Article abstract of DOI:10.1016/j.jorganchem.2005.09.009

The synthesis of the first series of 4-mono and 3,5-bis(dimethylamino) methyl-functionalized triarylphosphanes of the general formula PPh _{3 - n}Ar_n (Ar = 1-C₆H₃(CH ₂NMe₂)₂-3,5 (NC

Full text of DOI:10.1016/j.jorganchem.2005.09.009

Journal of Organometallic Chemistry 691 (2006) 422–432
www.elsevier.com/locate/jorganchem
Synthesis, coordination chemistry, and metal complex reactivity
of (dimethylamino)methyl-substituted triarylphosphanes; X-ray
study on [AuCl(PPh3 ꢀ nArn)] (Ar = 1-C6H3(CH2NMe2)2-3,5,
n = 1, 3; Ar = 1-C6H4(CH2NMe2)-4, n = 3)
a
a
a
b
b
Robert Kreiter , Judith J. Firet , Michel J.J. Ruts , Martin Lutz , Anthony L. Spek ,
a,
a,
*
Robertus J.M. Klein Gebbink *, Gerard van Koten
a
Debye Institute, Organic Chemistry and Catalysis, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands
Bijvoet Center for Biomolecular Research, Crystal and Structural Chemistry, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands
b
Received 14 July 2005; received in revised form 31 August 2005; accepted 5 September 2005
Available online 19 October 2005
Abstract
The synthesis of the first series of 4-mono and 3,5-bis(dimethylamino)methyl-functionalized triarylphosphanes of the general formula
PPh3 ꢀ nArn (Ar = 1-C6H3(CH2NMe2)2-3,5 (NC(H)N), n = 1 (ligand 2) or n = 3 (ligand 4); Ar = 1-C6H4(CH2NMe2)-4 (NC(H)), n = 3
(ligand 7)) is described. These phosphanes were used for the construction of complexes of the form [AuCl(P)] and [PtCl2(P)2]. In these
complexes selective coordination of phosphorus to the metal ion is observed. The 31P NMR data show the formation of cis-Pt complexes,
even in the case of triarylphosphane 4, which features a tris{3,5-bis(dimethylamino)methyl} substitution pattern. The structure of the
gold complex of mono-3,5-functionalized triarylphosphane 2 in the solid state shows a striking resemblance to the structure of the cor-
responding complex [AuCl(PPh3)]. The solid-state structure of the AuCl complex of tris-4-functionalized ligand 7 differs from that of
[AuCl(PPh3)] in the sign of the torsion angles. The amine functionalities in this class of gold compounds could be reacted selectively with
either acid (HCl, H3PO4) to generate ammonium salts or with an alkylating agent (benzyl bromide) to afford benzyl ammonium salts,
without the violation of the Au–P bond.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Triarylphosphane; Amine; Au–P coordination; Pt–P coordination; Protonation; Alkylation
1. Introduction
substitutions to arrive at water-soluble phosphanes [2]; the
most successful example being tris-sulfonated triphenyl-
phosphane (TPPTS) applied in the Rhoˆne-Poulenc
biphasic hydroformylation. Substitution of triarylphos-
phanes with fluorous alkyl chains has made those suitable
for application in fluorous biphasic catalysis [3]. Further-
more, many examples apply increased steric bulk on the phe-
nyl fragments thus rendering the ligands suitable candidates
for high turnover C–C, C–N, or C–O coupling reactions [4].
The functionalization of arylphosphanes with potentially
ligating groups opened up a new field of research, leading
the way for secondary (ligand-to-metal) interactions or the
formation of mixed metal complexes [5]. Examples of such
ligands are the 2,6-bis(dimethylamino)methyl-substituted
Phosphorus-based ligands have found many applica-
tions, both in coordination chemistry and in homogeneous
catalysis [1]. Among these, triphenylphosphane and its
numerous derivatives are key examples that were imple-
mented in many industrial applications. The reported
triphenylphosphane modifications include anion or cation
*
Corresponding authors. Tel.: +31 30 253 1889; fax: +31 30 2523615
(R.J.M. Klein Gebbink), Tel.: +31 30 2533120; fax: +31 30 2523615
(G. van Koten).
E-mail addresses: r.j.m.kleingebbink@chem.uu.nl (Robertus J.M. Klein
Gebbink), g.vankoten@chem.uu.nl (G. van Koten).
0022-328X/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.09.009

R. Kreiter et al. / Journal of Organometallic Chemistry 691 (2006) 422–432
423
amino)methyl-functionalized triarylphosphanes and shows
selective coordination of the phosphorus center in these li-
gands to gold(I) chloride and platinum(II) dichloride.
Moreover, protonation and quaternization with alkyl ha-
lides of the CH2NMe2-functionalities is discussed.
2. Results
2.1. Preparative results
Using a previously described protocol [8], mono{3,5-
bis[(dimethylamino)methyl]phenyl}-diphenylphosphane
(2, PPh2–(NC(H)N)) and tris{3,5-bis[(dimethylamino)-
methyl]phenyl}phosphane (4, P(NC(H)N)3) were prepared.
The procedure started from 1-bromo-3,5-bis[(dimethyla-
mino)methyl]benzene (1, Br–(NC(H)N)) [9], which was
converted into the respective phosphanes 2 and 4 via lith-
ium–bromide exchange followed by reaction with chlorodi-
phenylphosphane or phosphorus tribromide (Scheme 1). In
the case of 2, the crude product was obtained as a yellow
oil, which could be purified by bulb-to-bulb distillation,
affording the pure phosphane as a dark yellow oil in a yield
of 71%. In the case of hexa-functionalized ligand 4, the
product was partially oxidized to phosphane oxide 3 during
work-up of the reaction. Therefore, the crude product was
completely oxidized with H2O2 in THF, and after isolation
reduced to free phosphane 4 by treatment with HSiCl3 and
NEt3 in refluxing benzene. This procedure afforded pure 4
as a light yellow sticky solid. Both ligands feature a triaryl-
phosphane core having a 3,5-bis(dimethylamino)methyl
substitution pattern on one or all three of the aryl rings.
This moiety is potentially useful as a terdentate NCN-
pincer ligand, which is able to bind as a mono-anion to a
metal site [10].
Fig. 1. Examples of (dimethylamino)methyl-substituted arylphosphanes
reported by Cowley [6] (a), Corriu [7] (b), and in this report (c, d).
arylphosphanes (Fig. 1), reported by the groups of Cowley
(a) [6] and Corriu (b) [7]. They showed that intramolecular
N ! P coordination in this type of mixed ligands takes
place.
In our research, we set out to design and prepare bifunc-
tional arylphosphanes of the general formula PPh3 ꢀ nArn
(Ar = 1-C6H3(CH2NMe2)2-3,5 (NC(H)N); or Ar = 1-C6H4-
(CH2NMe2)-4 (NC(H))) (Fig. 1(c) and (d)) which on the one
hand could function as typical triarylphosphane ligands,
i.e., coordinate via the phosphorus center to a metal ion,
while at the same time being substituted with (dimethyl-
amino)methyl groups at either the para- or at both meta-
positions. The latter NC(H)N-motif could serve either for
the introduction of a metal atom via a M–C-bond (via bis-
ortho-metalation or transmetalation) or for the use as Lewis
basic functionalities (CH2NMe2), i.e., as extension of the
triarylphosphane scaffold by quaternization or by revers-
ible protonation/deprotonation. This paper discusses the
synthesis of the first series of 4-mono and 3,5-bis(dimethyl-
The corresponding tris{4-[(dimethylamino)methyl]-
phenyl}phosphane (7, P(NC(H))3) was prepared in a simi-
lar fashion (Scheme 2). Lithiation of 4-bromobenzylamine
Scheme 1. Synthesis of 3,5-bis(dimethylamino)methyl-substituted triarylphosphanes, PPh2–(NC(H)N) (2) and P(NC(H)N)3 (4).

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R. Kreiter et al. / Journal of Organometallic Chemistry 691 (2006) 422–432
Scheme 2. Synthesis of 4-(dimethylamino)methyl-substituted triarylphosphane P(NC(H))3 (7).
followed by a quench with phosphorus tribromide and sub-
sequent oxidation afforded phosphane oxide 6. The free
phosphane 7 was obtained after reduction.
P(NC(H)N)3 (4) was subjected to the same coordination
experiments (Scheme 3), using toluene as solvent for the
preparation of Au(I) complex 10. 1H and 31P NMR
analysis of 10 provided evidence for selective phosphane
coordination. By reaction of 4 with [PtCl2(COD)], cis-
[PtCl2(P(NC(H)N)3)2] (11; 31P NMR: d = 14.7 ppm,
1J(195Pt–31P) = 3661 Hz) was obtained. Apparently, func-
tionalization of all three aryl rings at the 3- and 5-positions
does not impose sufficient steric strain on the complex to
In order to study the coordination behavior of the phos-
phanes PPh2–(NC(H)N) (2), P(NC(H)N)3 (4), and
P(NC(H))3 (7), they were reacted with Au(I) and Pt(II) me-
tal complexes. To this end, ligand 2 was mixed with one
equivalent of [AuCl(THT)] in CH2Cl2. After overnight stir-
ring and removal of all volatiles a white solid material was
isolated. A shift of the 31P NMR signal from ꢀ3.8 ppm for
1
hamper the formation of a cis-complex. In the H NMR
1
2 to 31.9 ppm for 8 was observed. Furthermore, in the H
spectra of these complexes no additional interactions of
the amine substituents with Au(I) or Pt(II) were observed,
which follows the expected preference of Au(I) and Pt(II)
for coordination to the softer phosphorus site over the
binding to hard tertiary amine donor sites.
NMR spectra the resonance of the NMe2 protons was
unaffected. This indicated that the amine substituents were
not involved in coordination, leading to the conclusion that
[AuCl(PPh2–(NC(H)N))] (8, Scheme 3) was formed selec-
tively.
P(NC(H))3 (7) was reacted with [AuCl(THT)] in toluene
to afford the corresponding Au(I) complex [AuCl(P(NC-
(H))3)] (12) in high yield. Similar to the results for
complexes 8 and 10, the CH2NMe2 substituents in 12 did
not interact with Au(I) (cf. 1H and 31P NMR spectra).
Reaction of 7 with [PtCl2(COD)] resulted in quantitative
formation of cis-[PtCl2(P(NC(H))3)2] (13; 31P NMR:
In a parallel experiment, two equivalents of 2 were re-
acted with [PtCl2(COD)] in CH2Cl2 to afford the product
as a light yellow oil (Scheme 3). The 31P NMR spectrum
of 9 in CDCl3 showed a sharp resonance at 15.0 ppm with
a coupling constant of 1J(195Pt–31P) = 3660 Hz, pointing to
9 being a cis-complex. These data are in concert with those
found for the corresponding complex cis-[PtCl2(PPh3)2],
obtained by reaction of PPh3 with [PtCl2(COD)] (31P
NMR: d = 14.4 ppm, 1J(195Pt–31P) = 3674 Hz) [11]. The
possible other isomer, having a trans-geometry, was not
1
d = 13.5 ppm, J(195Pt–31P) = 3677 Hz) (Scheme 3).
2.2. Structures of [AuCl(PPh2–(NC(H)N))] (8) and
[AuCl(P(NC(H))3)] (12)
1
observed. In the H NMR spectrum of 9, no significant
shift is observed for the NMe2-protons indicating again
that no interaction between nitrogen and platinum takes
place. Therefore, we conclude that cis-Pt complex 9 is
formed selectively.
Colorless single crystals of 8, suitable for X-ray diffrac-
tion, were obtained via recrystallization from a pentane/
CH2Cl2 (3/1, v/v) mixture, while colorless single crystals
of 12 were prepared by slow evaporation of a C6D6
Scheme 3. Preparation of Au(I) complexes 8, 10, and 12 and cis-Pt(II) complexes 9, 11, and 13.

R. Kreiter et al. / Journal of Organometallic Chemistry 691 (2006) 422–432
425
Cl1
Au1
C19
C119
C118
C117
C16
C5
C113
Au
C17
C12
P1
C113
C124
C13
P
C18
N11
C116
C114
C11
C119
C14
C11
C1
C16
C123
C15
C115
C120
C110
C122
N12
C111
C121
C112
Fig. 2. Displacement ellipsoid plot (50% probability) of one of the two independent molecules of [AuCl(PPh2–(NC(H)N))] (8) (hydrogen atoms are
omitted for clarity) and a quaternion fit of both the triphenylphosphane-gold chloride fragments of [AuCl(PPh2–(NC(H)N))] (8, gray C-atoms) and
[AuCl(PPh3)] (black C-atoms), seen along the P–Au bond. The (NC(H)N)-fragment (C11–C16) is marked with a gray circle.
solution of this complex. The unit cell of 8 contains two
independent molecules that differ slightly in torsion angles
of the aryl fragments with respect to the P–Au bond (one of
the two independent molecules is shown in Fig. 2). The
PPh2–(NC(H)N) ligand is coordinated to the Au-center
trans to the chloride ion and the three aryl fragments have
a propeller-like arrangement. Secondary interactions or
intermolecular close-contacts are not observed, which indi-
cates that the CH2NMe2 substituents are free. Comparison
of the obtained molecular structure of 8 with the previously
reported structure of [AuCl(PPh3)] [12] shows a striking
similarity (Table 1). A quaternion fit of both triphenyl-
phosphane-gold chloride fragments of these complexes
underlines this equivalence (Fig. 2) [12]. Only slight differ-
ences in the interatomic distances, bond angles, and torsion
angles are observed, which indicates that the presence of
the single 3,5-bis[(dimethylamino)methyl] substitution
pattern in 8 leaves the primary structure of the [AuCl-
(PPh2Ar)] scaffold unaffected.
The structure of 12 in the solid state shows a propeller-
shaped complex having a diagonally coordinated gold cen-
ter and an exact, crystallographic threefold rotation axis
about the P–Au–Cl-axis (P–Au–Cl: 180ꢁ by symmetry)
(Fig. 3). Again, no interactions between the dimethylamino
Table 1
Selected interatomic distances and angles of [AuCl(PPh2–(NC(H)N))] (8),a [AuCl(P(NC(H))3)] (12), and [AuCl(PPh3)] [12]
[AuCl(PPh2(N(H)CN))] (8)
[AuCl(P(NC(H))3)] (12)
[AuCl(PPh3)]
˚
Bond lengths (A)
Au1–Cl1
Au1–P1
P1–C11
P1–C119
P1–C113
2.2789(6)
2.2289(6)
1.810(2)
1.811(3)
1.821(2)
Au1–Cl1
Au1–P1
P1–C1
2.272(2)
2.231(2)
1.814(2)
Au1–Cl1
Au1–P1
P1–C1
P1–C5
P1–C16
2.278
2.233
1.799
1.788
1.858
Angles (ꢁ)
P1–Au1–Cl1
Au1–P1–C11
Au1–P1–C119
Au1–P1–C113
C113–P1–C11
C119–P1–C11
C113–P1–C119
178.34(2)
P1–Au1–Cl1
Au1–P1–C1
180
112.00(10)
P1–Au1–Cl1
Au1–P1–C1
Au1–P1–C5
Au1–P1–C16
C16–P1–C1
C5–P1–C1
179.71
114.72
112.41
113.66
103.00
106.60
105.56
114.57(8)
112.88(8)
111.61(8)
104.20(11)
106.41(11)
106.46(14)
C1–P1–C1a
106.82(11)
C16–P1–C5
Torsion (ꢁ)
Au1–P1–C11–C12
Au1–P1–C113–C118
Au1–P1–C119-C124
a
36.3(2)
53.8(2)
26.7(2)
Au1–P1–C1–C6
ꢀ39.8
Au1–P1–C5–C6
Au1–P1–C16–C4
Au1–P1–C1–C15
38.78
58.16
29.88
Only one of the two independent molecules is considered.

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R. Kreiter et al. / Journal of Organometallic Chemistry 691 (2006) 422–432
Cl1
Au1
C1b
C6
C1
C16
Au C5
C1c
P1
C5
N1
C9
P
C8
C4
C7
C1a
C1*
C2
C3
Fig. 3. Displacement ellipsoid plot (50% probability) of [AuCl(P(NC(H))3)] (12) (hydrogen atoms are omitted for clarity) and a quaternion fit of both the
triphenylphosphane-gold chloride fragments of [AuCl(P(NC(H))3)] (12, gray C-atoms; C1a, C1b, C1c) and [AuCl(PPh3)] (black C-atoms; C1*, C5, C16),
seen along the P–Au bond.
groups and the gold atom are observed. Compared to the
structure of [AuCl(PPh3)] the bond lengths and C–P–C an-
gles are very similar. A quaternion fit of 12 and
[AuCl(PPh3)] reveals a difference in sign of the Au–P–
C1–C2 torsion angles (Fig. 3), whereas the magnitude of
those angles is similar.
the amine groupings with an alkyl halide. A small excess
(calculated with respect to the CH2NMe2 equivalents in
these complexes) of benzyl bromide was added to both
complexes (Scheme 4). 1H and 31P NMR spectroscopic
analysis of these reactions showed that, in both cases, the
phosphorus–gold(I) bond remains unaffected (31P NMR,
CD3OD, d = 36.4 ppm for 14, d = 39.4 ppm for 15), and
that full conversion to the N-per-alkylated species occurs.
Interestingly, the 31P NMR chemical shift for bis-function-
alized 14 lies significantly more downfield compared to that
of hexa-functionalized 15. The solubility of both these
2.3. Alkylation and protonation of 8, 10, and 12
To investigate if the NC(H)N manifold in 8 and 10 is
available for reaction, we chose the alkylation reaction of
Scheme 4. Reaction of 8 and 10 with benzyl bromide to afford 3,5-bis-ammonium-substituted triarylphosphane gold(I) chloride complexes 14 and 15,
respectively.

R. Kreiter et al. / Journal of Organometallic Chemistry 691 (2006) 422–432
427
Scheme 5. Reaction of 12 with benzyl bromide, HCl, and H3PO4.
alkylated complexes changes dramatically from soluble in
chlorinated organic solvents to soluble only in polar sol-
vents like MeOH and EtOH.
in 31P NMR, we assume that a polymeric network was
formed rather than a tricationic triarylphosphane structure
with discrete, separate entities (Scheme 5).
[AuCl(P(NC(H))3)] (12) was also reacted with a small
excess of benzyl bromide (Scheme 5), affording the tris-
ammonium salt 16 selectively, as was confirmed by 1H
and 31P NMR data. The 31P NMR shift for 16 (CD3OD,
d = 39.3 ppm) is very similar to that of 15 (CD3OD,
d = 39.4 ppm), despite the differences in substitution pat-
tern (4-mono compared to 3,5-bis) and in number of
ammonium groups (3 compared to 6). Reaction of a small
excess of HCl in Et2O with 12 dissolved in CH2Cl2 resulted
in the formation of a white precipitate (17, Scheme 5). The
product was highly hygroscopic and soluble in H2O. In the
1H NMR spectrum, the signal corresponding to the NMe2
fragment shifts from 1.95 (in C6D6) to 2.7 ppm (in D2O)
upon protonation, while the 31P NMR spectrum confirmed
the phosphane-gold complexation (D2O, d = 33.0 ppm).
Upon dropwise addition of a solution of H3PO4 in acetone
to 12, dissolved in CH2Cl2, a white precipitate slowly
formed. The 31P NMR spectrum of the product in D2O,
in which it is slightly soluble, showed two clear, but rela-
tively broad signals, representing the P–Au (d = 29.7)
and PO34ꢀ (d = ꢀ0.1 ppm) phosphorus atoms. Based on
the low solubility of 18 in water as well as the broad signals
3. Discussion
This report presents the synthesis and coordination
chemistry of 4-mono and 3,5-bis[(dimethylamino)methyl]-
phenylphosphanes. The NMR spectra of these aminophos-
phane ligands show no signs of N ! P interactions (cf.
Fig. 1(a) and (b)). This can be explained by the substitution
pattern, which imposes inter- rather than energetically
more favorable intramolecular coordination [6,7].
Coordination of the ligands 2, 4, and 7 to Au(I) and
Pt(II) shows that they behave as pure phosphane donor li-
gands towards these ions, and that the amino substituents
are not involved in the coordination. This is supported by
the solid state structures of the gold complexes 8 and 12.
Multiple 3,5-bis-substitution of so-called BIPHEP (2,2-
bis(diarylphosphanyl)biphenyl) ligands leading to
a
ꢀmeta-effectꢁ in catalysis was reported by Pregosin et al.
[13]. In that case the meta-substitution pattern resulted in
the formation of a more rigid and slightly larger chiral
pocket in the corresponding Ru-complex. In our case, the
exclusive formation of cis-complexes in the case of the

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R. Kreiter et al. / Journal of Organometallic Chemistry 691 (2006) 422–432
PtCl2 bisphosphane complexes 9 and 11 seems unaffected
by the presence of 3,5-bis-substitution. The solid state
structure of complex 8, which is almost identical to that
of the corresponding PPh3 complex, supports this observa-
tion. Interestingly, this exclusive formation of a cis-plati-
num dichloride complex in the case of 6 is in contrast
with the findings for its previously reported hexa-ammo-
nium salts (Dendriphos) [8], for which increased bulk and,
presumably, larger cone angles lead to the exclusive forma-
tion of the trans-platinum dichloride complexes [14]. The
similarity of 8 and [AuCl(PPh3)] in the solid state is in line
with the observations of Dunitz, who discussed the struc-
ture of triphenylmethane and triphenylphosphane stereo-
isomers in the solid state [15]. Generally, such molecules
will adopt slightly distorted C3-symmetric conformations.
The observed C3-symmetric solid state feature of the 4-
mono-functionalized complex 12 follows those predictions.
It differs from the structure of [AuCl(PPh3)] mainly in the
sign of the Au–P–C1–C2 torsion angles, i.e., the other ste-
reoisomer was found. In solution, the formation of a cis-
platinum bisphosphane complex in the case of 13, and
the similarity of the 31P NMR spectra of 9, 11, and 13 sug-
gest that there are no significant differences in steric
behavior.
The experiments with Au(I) complexes 8, 10, and 12
show that the phosphorus center is effectively protected
by the Au–P coordination, allowing selective functionaliza-
tion of the amino substituents with either an alkyl halide or
an acid. The benzyl bromide salts 14, 15, and 16 represent
coordination complexes that have a relatively high polar
character (soluble in MeOH), while the HCl salt 17 is water
soluble. The protonation of 12 to afford 17 demonstrates
the use of the amino-ꢀhandleꢁ in 12 for facile transfer of a
gold-phosphane coordination complex to an aqueous
environment. This hints at the application of these ligands
in aqueous phase or phase transfer catalysis. Reaction of 12
with exactly one-third equivalent of the tri-acid H3PO4, in
principle, could have lead to selective formation of tris-
ammonium salt entities of the formula [AuCl-
(P(NC(H))3)H3]PO4. In this case, however, the formation
of a very poorly soluble product points to the formation
of a polymeric network. This procedure provides a means
for facile recovery of such gold(I) phosphane complexes
from almost any solvent, by addition of a dilute solution
of H3PO4.
structural features. Complexation to gold provides excel-
lent protection for the phosphane center, allowing subse-
quent reactions of the amine functionalities with an alkyl
halide or with acid. Further investigations on these com-
pounds focus on the application of these ligands in aqueous
media and on their phase transfer behavior.
5. Experimental
5.1. General
All air and moisture sensitive experiments were con-
ducted under a dry nitrogen atmosphere using standard
Schlenk techniques. Solvents for these manipulations were
dried over appropriate materials and distilled prior to use.
1-Bromo-3,5-bis[(dimethylamino)methyl]benzene (1) [9],
tris{3,5[(dimethylamino)methyl]phenyl}phosphane oxide
(3) [8], 1-bromo-4-[(dimethylamino)methyl]benzene (5)
[16], [PtCl2(COD)] [17], and [AuCl(THT)] [18] were pre-
pared via the literature procedures. 1H, 13C, and 31P
NMR spectra were recorded at 298 K on a Varian Mercury
200 MHz or a Varian Inova 300 MHz spectrometer. All 1H
and 13C NMR chemical shifts are in ppm referenced to the
residual solvent signal and all 31P NMR chemical shifts are
referenced against H3PO4 as external standard. MS data
were collected on an Applied Biosystems Voyager System
mass spectrometer (MALDI-TOF MS). ESI-MS spectra
were recorded on a Micromass LC-T mass spectrometer.
Elemental analyses were performed by Kolbe, Mulheim
¨
a/d Ruhr, Germany.
5.2. Synthesis
5.2.1. Synthesis of {3,5-bis[(dimethylamino)methyl]-
phenyl}diphenylphosphane, (PPh2–(NC(H)N), 2)
To a solution of 1-bromo-3,5-bis[(dimethylamino)-
methyl]benzene (1) (3.30 g, 11.90 mmol) in dry Et2O
(75 mL) was added dropwise t-BuLi (16.30 mL, 1.5 M in
pentane, 24.50 mmol) at ꢀ78 ꢁC, resulting in a beige sus-
pension. After stirring for 30 min at ꢀ78 ꢁC Ph2PCl
(2.40 mL, 13.20 mmol) was added and the mixture was al-
lowed to warm to room temperature overnight. Degassed
NaOH (15 mL, 4 M) was slowly added at 0 ꢁC until
pH > 10, followed by removal of all volatiles. The result-
ing aqueous layer was extracted with CH2Cl2
(3 · 40 mL) and to the combined organic fractions HBF4
(2.74 mL, 54 wt% Et2O, 23.80 mmol) was added, followed
by addition of H2O (15 mL) until a clear biphasic system
was obtained. The aqueous layer was washed with CH2Cl2
(3 · 30 mL) and degassed NaOH (15 mL, 4 M) was slowly
added at 0 ꢁC until pH > 10. The product was extracted
with CH2Cl2 (4 · 30 mL) and the combined organic frac-
tions were dried over MgSO4. All volatiles were evapo-
rated in vacuo followed by Kugelrohr distillation
(100 ꢁC, 0.1–0.2 mm Hg) affording a dark yellow oil.
Yield: 3.18 g (71%). 1H NMR (C6D6, 300 MHz):
d = 7.44 (m, 6H, ArH), 7.00 (m, 7H, ArH), 3.15 (s, 4H,
4. Conclusions
The presented 3,5-bis and 4-mono(dimethylamino)-
methyl-functionalized triarylphosphanes, coordinate to
Au(I) and Pt(II) via selective phosphorus–metal coordi-
nation. The similarity of Au(I) complexes of these
CH2NMe2-substituted triarylphosphanes to the parent tri-
phenylphosphane complex is apparent from the bond
lengths and C–P–C angles in the obtained crystal struc-
tures. The PtCl2 complexes 11 and 13 show that in solution
the 4- and the 3,5-bisfunctionalized ligands have similar

R. Kreiter et al. / Journal of Organometallic Chemistry 691 (2006) 422–432
429
CH2N), 1.98 (s, 12H, N(CH3)2); 13C NMR (C6D6,
were removed in vacuo. The resulting aqueous mixture
was extracted with CH2Cl2 (2 · 50 mL) and the combined
organic layers were dried on Mg2SO4, filtered and evapo-
rated to dryness. The product was obtained as a white
microcrystalline solid by precipitation from Et2O. Yield:
3
75 MHz): d = 140.19 (d, JPC = 7.3 Hz, ArC), 138.34 (d,
1
1JPC = 12.8 Hz, PhC), 137.47 (d, JPC = 11.6 Hz, ArC),
134.00
(d,
2JPC = 19.4 Hz,
PhC),
133.30
(d,
2JPC = 20.0 Hz, ArC), 130.33 (ArC), 128.65 (PhC),
3
1
128.64 (d, JPC = 6.7 Hz, PhC), 64.02 (s, CH2N), 45.14
2.41 g (71%). H NMR (C6D6, 200 MHz): d = 7.43 (dd,
(s, N(CH3)2); 31P NMR (C6D6, 81 MHz): d = ꢀ3.84;
MALDI-TOF MS: m/z 377.38 [M + H]+ (82%). Anal.
Calc. for C24H29N2P: C, 76.57; H, 7.76; N, 7.44; P, 8.23.
Found: C, 76.64; H, 7.68; N, 7.36; P, 8.20%.
3JHH = 11.4 Hz, JPH = 8.2 Hz, 6H, ArH), 7.22 (dd,
3
4
3JHH = 7.6 Hz, JPH = 2.4 Hz, 6H, ArH), 3.09 (s, 6H,
CH2N), 1.95 (s, 18H, N(CH3)2); 13C NMR (C6D6,
3
50 MHz): d = 143.34 (d, JPC = 3.0 Hz, ArC), 134.17
2
(ArC), 132.33 (d, JPC = 10.2 Hz, ArC), 128.78 (d,
5.2.2. General procedure for the reduction of
1JPC = 11.7 Hz, ArC), 63.90 (s, CH2N), 45.34 (N(CH3)2);
31P NMR (C6D6, 81 MHz): d = 25.56; MALDI-TOF MS:
m/z 450.40 [M + H]+ (100%). Anal. Calc. for C27H36N3OP:
C, 72.13; H, 8.07; N, 9.35; P, 6.89. Found: C, 71.96; H,
7.93; N, 9.27; P, 6.75%.
(dimethylamino)methyl-substituted triarylphosphane oxides
HSiCl3 (10 equiv.) and NEt3 (10 equiv.) were added to
a solution of the phosphane oxide in dry C6H6 and the
mixture was heated to reflux temperature for 2 h. After
cooling to room temperature, the mixture was neutral-
ized by dropwise addition of a saturated aqueous
solution of NaHCO3 and the organic layer was removed
in vacuo. The aqueous layer was extracted twice with
CH2Cl2 and the combined organic fractions were dried
on Mg2SO4, filtered, and evaporated to dryness, afford-
ing the pure phosphane as a light yellow sticky solid.
5.2.5. Synthesis of tri{4-[(dimethylamino)methyl]phenyl}-
phosphane (P(NC(H))3, 7)
Starting from 6 (1.20 g, 2.67 mmol) in dry C6H6
(40 mL) by addition of HSiCl3 (2.71 mL, 26.8 mmol)
1
and NEt3 (3.75 mL, 26.8 mmol). Yield: 1.11 g (96%). H
NMR (CDCl3, 200 MHz): d = 7.26, 7.24 (overlapping
doublets, 12H, ArH), 3.40 (s, 6H, CH2N), 2.22 (s, 18H,
N(CH3)2); 13C NMR (CDCl3, 50 MHz): d = 139.73
5.2.3. Synthesis of tri{3,5-bis[(dimethylamino)methyl]-
phenyl}phosphane (P(NC(H)N)3, 4)
3
(ArC), 136.09 (d, JPC = 9,7 Hz, ArC), 133.81 (d,
1
Starting from 3 (1.37 g, 2.21 mmol) in dry C6H6 (40 mL)
by addition of HSiCl3 (2.2 mL, 21.7 mmol) and NEt3
(3.1 mL, 22.1 mmol). Yield: 0.85 g (64%). 1H NMR
(CDCl3, 200 MHz): d = 7.24 (s, 3H, ArH), 7.08 (dd, 6H,
2JPC = 19,9 Hz, ArC), 129.21 (d, JPC = 21.2 Hz, ArC),
64.37 (CH2N), 45.74 (N(CH3)2); 31P NMR (CDCl3,
81 MHz): d = ꢀ6.16; MALDI-TOF MS: m/z 434.47
[M + H]+ (100%). Anal. Calc. for C27H36N3P: C, 74.80;
H, 8.37; N, 9.69; P, 7.14. Found: C, 74.67; H, 8.32; N,
9.74; P, 7.19%.
4
3JPH = 7.6 Hz, JHH = 1.4 Hz, ArH), 3.30 (s, 12H,
CH2N), 2.14 (s, 36H, N(CH3)2); 13C NMR (CDCl3,
3
75 MHz): d = 138.98 (d, JPC = 6.7 Hz, ArC), 137.39 (d,
1
2JPC = 11.6 Hz, ArC), 133.56 (d, JPC = 14.6 Hz, ArC),
5.2.6. Synthesis of [AuCl(PPh2–(NC(H)N))] (8)
solution of PPh2–(NC(H)N) (2; 114.0 mg,
130.71 (ArC), 64.21 (CH2N), 45.60 (N(CH3)2); 31P NMR
(CDCl3, 81 MHz): d = ꢀ5.44 (s); MALDI-TOF MS: m/z
605.66 [M + H]+ (100%). Anal. Calc. for C36H57N6P: C,
71.49; H, 9.50; N, 13.89; P, 5.12. Found: C, 71.37; H,
9.43; N, 13.72; P, 5.08%.
A
0.30 mmol) in CH2Cl2 (20 mL) was slowly added to a
solution of [AuCl(THT)] (87.0 mg, 0.30 mmol) in CH2Cl2
(10 mL) and the mixture was stirred for 16 h at room
temperature protected from sunlight. All volatiles were
evaporated in vacuo affording a light yellow oil. Yield:
0.17 g (93%). Colorless crystals, suitable for X-ray dif-
fraction, were obtained by addition of pentane (20 mL)
to a solution of 6 in CH2Cl2 (10 mL) after overnight
standing at room temperature. 1H NMR (C6D6,
300 MHz): d = 7.57 (s, 1H, ArH), 7.49 (d, 2H,
5.2.4. Synthesis of tri{4-[(dimethylamino)methyl]-
phenyl}phosphane oxide (P(O)(NC(H))3, 6)
t-BuLi (30.21 mL, 1.5 M in pentane, 45.31 mmol) was
added dropwise to a solution of 1-bromo-4-(dimethyl-
amino)methylbenzene (7; 4.85 g, 22.65 mmol) in dry Et2O
(40 mL) at ꢀ78 ꢁC and the resulting light brown suspen-
sion was stirred for 45 min. PBr3 (0.71 mL, 7.55 mmol)
was added dropwise and the mixture was allowed to warm
up to room temperature over 16 h. H2O (40 mL) was added
carefully and the organic layer was separated. The aqueous
layer was extracted with CH2Cl2 (3 · 30 mL) and the com-
bined organic fractions were dried over Mg2SO4, filtered
and evaporated to dryness. Kugelrohr distillation at
100 ꢁC (0.1–0.2 mm Hg) was applied for 2 h, after which
the product was dissolved in THF (50 mL) and H2O2
(0.20 mL, 35% in H2O) was added. The mixture was stirred
for 2 h, NaOH (50 mL, 1M) was added and all volatiles
3
3JPH = 9.9 Hz, ArH), 7.38 (dd, 4H, JHH = 11.7 Hz,
4JPH = 4.2 Hz, ArH), 6.99 (m, 6H, ArH), 3.09 (s, 4H,
CH2N), 1.96 (s, 12H, N(CH3)2); 13C NMR (C6D6,
3
75 MHz) d = 141.09 (d, JPC = 11.0 Hz, ArC), 134.17
2
2
(d, JPC = 14.0 Hz, PhC), 133.16 (d, JPC = 15.2 Hz,
1
ArC), 132.41 (ArC), 131.25 (d, JPC = 50.3 Hz, PhC),
131.05 (PhC), 130.57 (d, JPC = 47.3 Hz, ArC), 129.05 (d,
1
3JPC = 11.0 Hz, PhC), 63.47 (CH2N), 45.08 (N(CH3)2);
31P NMR (C6D6, 81 MHz): d = 31.89; MALDI-
TOF MS: m/z 609.19 [M + H]+ (100%). Anal. Calc. for
C24H29N2PAuCl: C, 47.34; H, 4.80; N, 4.60; P, 5.10.
Found: C, 47.52; H, 4.76; N, 4.55; P, 5.13%.

430
R. Kreiter et al. / Journal of Organometallic Chemistry 691 (2006) 422–432
5.2.7. Synthesis of cis-[PtCl2(PPh2–(NC(H)N))2] (9)
A solution of PPh2–(NC(H)N) (2; 94.4 mg, 0.25 mmol)
and the mixture was stirred for 16 h at room temperature,
resulting in a dark purple solution. The crude mixture was
filtered over celite and evaporated to dryness. The resulting
off-white solid was purified further by precipitation from a
CH2Cl2/hexane (1/10, v/v) mixture, resulting in a off-white
solid. Yield: 0.74 g (79%). Crystals, suitable for X-ray dif-
fraction were obtained by slow evaporation of a C6D6 solu-
in CH2Cl2 (20 mL) was added to
a solution of
[PtCl2(COD)] (47.0 mg, 125 lmol) in CH2Cl2 (20 mL),
and the mixture was stirred for 1 h at room temperature,
followed by heating to reflux temperature for 15 min.
CH2Cl2 and COD were removed in vacuo and a light
yellow oil was obtained. Yield: 0.12 g (96%). 1H NMR
(CDCl3, 200 MHz): d = 7.45–7.08 (overlapping, 13H,
ArH), 3.22 (s, 4H, CH2N), 2.09 (s, 12H, N(CH3)2); 13C
NMR (CDCl3, 75 MHz): d = 138.44 (broad, ArC),
134.91 (broad, PhC), 132.85 (ArC), 130.86 (PhC),
129.73 (1JPC = 64.5 Hz, ArC), 128.87 (overlapping d,
ArC), 128.54, 128.04 (PhC), 63.50 (CH2N), 45.24
(N(CH3)2); 31P NMR (CDCl3, 81 MHz): d = 15.04
(JPtP = 3660 Hz); MALDI-TOF MS: m/z 947.59
[M ꢀ 2Cl]+ (100%). Anal. Calc. for C48H58Cl2N4P2Pt:
C, 56.58; H, 5.74; N, 5.50; P, 6.08. Found: C, 56.51;
H, 5.84; N, 5.42; P, 6.04%.
1
tion of 12. H NMR (C6D6, 200 MHz): d = 7.3–7.0 (m,
12H, ArH), 3.05 (s, 6H, CH2N), 1.95 (s, 18H, N(CH3)2);
13C NMR (C6D6, 50 MHz): d = 143.89 (ArC), 134.14 (d,
3
2JPC = 14.1 Hz, ArC), 129.32 (d, JPC = 12.1 Hz, ArC),
1
128.33 (d, JPC = 27.0 Hz, ArC), 63.63 (CH2N), 45.44
(N(CH3)2); 31P NMR (C6D6, 81 MHz): d = 32.14; MALDI-
TOF MS: m/z 664.61 [M]+ (100%). Anal. Calc. for
C27H36AuClN3P: C, 48.69; H, 5.45; N, 6.31; P, 4.65.
Found: C, 48.72; H, 5.35; N, 6.26; P, 4.58%.
5.2.11. Synthesis of cis-[PtCl2(P(NC(H))3)2] (13)
To a solution of 7 (38.2 mg, 88.1 lmol) in dry CH2Cl2
(20 mL) was added a solution of [PtCl2(COD)] (16.5 mg,
44.1 lmol) and the mixture was stirred for 1 h at room tem-
perature, followed by heating to reflux temperature for
15 min. Subsequently, all volatiles were evaporated to dry-
ness, and the solid residue was washed with hexane, afford-
ing 13 as a light yellow solid in quantitative yield. 1H NMR
5.2.8. Synthesis of [AuCl(P(NC(H)N)3)] (10)
Solid [AuCl(THT)] (78.5 mg, 0.25 mmol) was added to
a solution of 4 (0.15 g, 0.25 mmol) in toluene (30 mL) and
the mixture was stirred for 30 min at room temperature.
The resulting light yellow solution was evaporated to dry-
ness, hexane was added and the solution was filtered.
Evaporation of the hexane filtrate afforded the product
as an off-white solid. Yield: 0.19 g (91%). 1H NMR
(C6D6, 200 MHz): d = 7.58, 7.52 (overlapping s and d,
9H, ArH), 3.01 (s, 12H, CH2N), 1.93 (s, 36H,
N(CH3)2); 13C NMR (C6D6, 50 MHz): d = 141.17 (d,
3
(CDCl3, 300 MHz): d = 7.41 (dd, 12H, JHH = 8.1 Hz,
3
2JPH = 10.8 Hz, ArH), 7.08 (d, 12H, JHH = 6.9 Hz,
ArH), 3.36 (s, 12H, CH2N), 2.20 (s, 36H, N(CH3)2); 13C
NMR (CDCl3, 50 MHz): d = 141.99 (ArC), 135.13 (d,
2
3JPC = 5.4 Hz, ArC), 128.49 (d, JPC = 5.8 Hz, ArC),
1
128.31 (d, JPC = 66.5 Hz, ArC), 63.50 (CH2N), 45.28
2
3JPC = 11.7 Hz, ArC), 133.14 (d, JPC = 14.5 Hz, ArC),
(N(CH3)2); 31P NMR (CDCl3, 121.5 MHz): d = 13.53 (t,
JPtP = 3677 Hz); MALDI-TOF MS: m/z 1062.23
[M ꢀ 2Cl]+. Anal. Calc. for C54H72Cl2N6P2Pt: C, 57.24;
H, 6.40; N, 7.42; P, 5.47. Found: C, 57.30; H, 6.33; N,
7.37; P, 5.35%.
1
132.69 (s, ArC), 129.68 (d, JPC = 59.7 Hz, ArC), 63.50
(CH2N), 45.12 (N(CH3)2); 31P NMR (C6D6, 81 MHz):
d = 33.42; MALDI-TOF MS: m/z 835.64 [M]+ (100%).
Anal. Calc. for C36H57AuClN6P: C, 51.64; H, 6.86; N,
10.04; P, 3.70. Found: C, 51.77; H, 6.89; N, 9.89; P,
3.85%.
5.2.12. Synthesis of [AuCl(PPh2–(NC(H)N)) Æ Bzl2]Br2
(14)
5.2.9. Synthesis of cis-[PtCl2(P(NC(H)N)3)2] (11)
To a solution of 4 (101.6 mg, 0.13 mmol) in dry CH2Cl2
was added solid [PtCl2(COD)] (24.4 mg, 65.1 lmol) and the
mixture was stirred for 1 h at room temperature, followed
by heating to reflux temperature for 15 min. Subsequently,
all volatiles were removed in vacuo, affording 11 as a light
yellow solid in quantitative yield. 1H NMR (CDCl3,
200 MHz): d = 7.4–7.2 (overlapping, 9H, ArH), 3.19 (s,
12H, CH2N), 2.09 (s, 36H, N(CH3)2); 13C NMR (CDCl3,
75 MHz): d = 138.29 (broad, ArC), 134.64 (broad, ArC),
To a solution of 8 (20.0 mg, 33.0 lmol) in CH2Cl2
(30 mL) was added dropwise benzyl bromide (0.80 mL,
0.084 M in CH2Cl2, 67.00 lmol). The colorless clear reac-
tion mixture was stirred overnight after which all volatiles
were removed and a white sticky residue was obtained. The
pure product was obtained by precipitation from a MeOH/
1
Et2O mixture (1/5, v/v). Yield: 29.5 mg (94%). H NMR
(CD3OD, 200 MHz): d = 8.3–7.4 (m, ArH), 4.77 (s,
CH2N), 4.68 (s, CH2Ph), 3.01 (s, N(CH3)2); 13C NMR
(CD3OD, 75 MHz): d = 141.03 (ArC), 140.00 (d,
1
2
132.18 (ArC), 129.58 (d, JPC = 66.5 Hz, ArC), 63.64
3JPC = 13.1 Hz, ArC), 134.72 (d, JPC = 14.6 Hz, PhC),
(CH2N), 45.36 (N(CH3)2); 31P NMR (C6D6, 81 MHz):
d = 14.66 (t, JPtP = 3641 Hz). MALDI-TOF MS: m/z
1403.92 [M ꢀ 2Cl]+ (100%).
134.49
(d,
2JPC = 14.25 Hz,
ArC),
133.51
(d,
1JPC = 30.0 Hz, ArC), 133.31, 132.69 (CH2PhC), 130.86
3
(PhC), 130.33 (d, JPC = 11.6 Hz, PhC), 129.69 (dd,
2JPC = 11.85 Hz, JCC = 3.3 Hz, PhC), 128.27 (dd,
1JPC = 69.0 Hz, JCC = 13.5 Hz, PhC), 129.15, 127.35
(CH2PhC), 68.41 (CH2N), 67.01 (PhCH2), 48.39
(N(CH3)2); 31P NMR (CD3OD, 81 MHz): d = 36.42;
5.2.10. Synthesis of [AuCl(P(NC(H))3)] (12)
Solid [AuCl(THT)] (0.45 g, 1.41 mmol) was added to a
solution of 7 (0.61 g, 1.41 mmol) in dry toluene (50 mL)

R. Kreiter et al. / Journal of Organometallic Chemistry 691 (2006) 422–432
431
4
ESI-MS: m/z 915.43 [M ꢀ Cl]+ (12%), 743.15
[M ꢀ Cl ꢀ C7H7Br]+. Anal. Calc. for C38H43AuBr2ClN2P:
C, 47.99; H, 4.56; N, 2.95; P, 3.26. Found: C, 47.56; H,
4.64; N, 2.78; P, 3.12%.
2JPC = 14.3 Hz, ArC), 133.89 (d, JPC = 2.7 Hz, ArC),
131.80 (d, 3JPC = 12.2 Hz, ArC), 129.86 (d, 1JPC = 64.5 Hz,
ArC), 60.33 (CH2N), 42.50 (d, J = 4.2 Hz, N(CH3)2); 31P
NMR (D2O, 121.5 MHz): d = 32.97; ESI-MS: m/z 703.42
[M ꢀ 2Cl]+ (30%), 333.75 [M ꢀ 3Cl]2+ (100%).
5.2.13. Synthesis of [AuCl(P(NC(H)N)3) Æ Bzl6]Br6 (15)
Benzyl bromide (27.0 lL, 0.23 mmol) was added drop-
wise to a solution of 10 (29.6 mg, 35.4 lmol) in CH2Cl2
(30 mL) and the mixture was stirred for 2 h at room tem-
perature. All volatiles were evaporated and the excess of
benzyl bromide was removed by precipitation of the prod-
uct from a MeOH/Et2O (1/3, v/v) mixture, affording a
white solid in quantitative yield. 1H NMR (CD3OD,
5.2.16. Protonation of 12 to afford [AuCl(P(NC(H))3) Æ
H3](PO4)n (18)
To a solution of 12 (50.7 mg, 76.13 lmol) in CH2Cl2
(15 mL) was added dropwise a solution of H3PO4 in acetone
(1.02 mL, 2.48 mg/mL, 25.3 lmol) and the mixture was stir-
red for 1 h. The resulting white suspension was evaporated
to dryness, affording the product as a white solid in quanti-
3
200 MHz): d = 8.70 (d, JPH = 12.0 Hz, 6H, ArH), 8.10
1
tative yield. H NMR (D2O, 200 MHz): d = 6.9–6.6 (over-
(s, 3H, ArH), 7.71, 7.68, 7.52, 7.49 (m, 30H, PhH), 4.79
(s, 12H, CH2N), 4.75 (s, 12H, PhCH2), 3.07 (s, 36H,
N(CH3)2); 13C NMR (CD3OD, 75 MHz): d = 141.95 (s,
lapping, 12H, ArH), 3.42 (s, 6H, CH2N), 1.90 (s, 18H,
N(CH3)2); 13C NMR: solubility too low to measure; 31P
NMR (D2O, 81 MHz): d = 29.66 (AuP), ꢀ0.05 ðPO3ꢀÞ.
2
ArC), 141.30 (d, JPC = 14.6 Hz, ArC), 133.51 (PhC),
4
ESI-MS m/z 1295.84 [2M ꢀ 2PO4 ꢀ Cl ꢀ 4H]+ (100%),
1
132.60 (d, JPC = 60.4 Hz, ArC), 130.83 (PhC), 130.71
666.38 [M ꢀ PO4 ꢀ 2H]+ (35%).
(ArC), 129.15, 127.60 (PhC); 31P NMR (CD3OD,
81 MHz): d = 39.44; ESI-MS: m/z 1828.73 [M ꢀ Cl]+,
874.99 [M ꢀ Cl ꢀ Br]2+ (45%), 556.34 [M ꢀ Cl ꢀ 2Br]3+
(100%). Anal. Calc. for C78H99AuBr6ClN6P: C, 50.27; H,
5.35; N, 4.51; P, 1.66. Found: C, 50.15; H, 5.42; N, 4.37;
P, 1.70%.
5.3. Crystal structure determination of 8 and 12
X-ray intensities were collected on a Nonius KappaCCD
diffractometer with rotating anode and Mo Ka radiation
(graphite monochromator, k = 0.71073 A) at a temperature
of 150(2) K up to a resolution of (sinh/k)max = 0.65 A
The structures were solved with automated Patterson meth-
ods [19] for 8 and with Direct Methods [20] for 12, and
refined with SHELXL-97 [21] against F2 of all reflections.
Non-hydrogen atoms were refined with anisotropic dis-
placement parameters. Hydrogen atoms were introduced
in calculated positions and refined as rigid groups. The
drawings, geometry calculations, and checking for higher
symmetry were performed with the program PLATON [22].
Crystal data for 8: C24H29AuClN2P, Fw = 608.88, color-
˚
5.2.14. Synthesis of [AuCl(P(NC(H))3) Æ Bzl3]Br3 (16)
Benzyl bromide (0.12 mL, 1.04 mmol) was added to a
solution of 12 (0.23 g, 0.34 mmol) in CH2Cl2 (50 mL) and
the mixture was stirred for 2 h at room temperature. All
volatiles were evaporated and the excess of benzyl bromide
was removed by repeated precipitation of the product from
a MeOH/Et2O (1/3, v/v) mixture, affording a white solid.
Yield: 0.37 g (93%). 1H NMR (CD3OD, 200 MHz):
ꢀ1
˚
.
3
d = 8.71 (d, JPH = 12.4 Hz, 6H, ArH), 8.12 (s, 6H,
ArH), 7.71, 7.68, 7.52, 7.49 (m, 15H, PhH) 4.84 (s, 6H,
CH2Ph), 4.76 (s, 6H, CH2N), 3.07 (s, 18H, N(CH3)2); 13C
3
ꢀ
less plate, 0.48 · 0.27 · 0.12 mm , triclinic, P1 ðNo. 2Þ,
2
NMR (CD3OD, 75 MHz): d = 135.15 (d, JPC = 14.3 Hz,
˚
˚
˚
3
a = 10.8697(1) A, b = 14.0294(1) A, c = 17.6771(2) A,
a = 91.6520(3)ꢁ, b = 107.6593(4)ꢁ, c = 109.7291(4)ꢁ, V =
ArC), 134.43 (d, JPC = 12.0 Hz, ArC), 133.31 (PhC),
4
1
132.13 (d, JPC = 2.8 Hz, ArC), 131.17 (d, JPC = 59.4 Hz,
ArC), 130.88, 129.23, 127.49 (PhC), 68.45 (CH2N), 67.38
(PhCH2), 48.68 (N(CH3)2); 31P NMR (D2O, 81 MHz):
d = 39.34; ESI-MS: m/z 1144.51 [M ꢀ Cl]+ (30%), 531.78
[M ꢀ Cl ꢀ Br]2+ (100%). Anal. Calc. for C48H57Au-
Br3ClN3P: C, 48.89; H, 4.87; N, 3.56; P, 2.63. Found: C,
48.87; H, 4.93; N, 3.39; P, 2.68%.
3
3
˚
2391.84(4) A , Z = 4, q = 1.691 g/cm . 48,519 Reflections
were measured. An analytical absorption correction was
applied (l = 6.34 mmꢀ1
, 0.13–0.64 correction range).
10,905 Reflections were unique (Rint = 0.048). 531 Parame-
ters were refined with no restraints. R1/wR2 [I > 2r(I)]:
0.0195/0.0440. R1/wR2 [all reflections]: 0.0246/0.0460.
S = 1.031. Residual electron density between ꢀ0.81 and
3
˚
1.00 e/A .
5.2.15. Protonation of 12 to afford [AuCl(P(NC(H))3) Æ
H3]Cl3 (17)
Crystal data for 12: C27H36AuClN3P, Fw = 665.97,
colorless needle, 0.48 · 0.12 · 0.09 mm3, hexagonal, P63
To a solution of 12 (32.2 mg, 48.3 lmol) in CH2Cl2 was
added HCl (1 M in Et2O, 0.1 mL). The mixture was stirred
for 15 min and all volatiles were evaporated, affording 17
as a light yellow solid in quantitative yield. 1H NMR
˚
˚
(No. 173), a = b = 13.1848(7) A, c = 9.0589(8) A, V =
3
3
˚
1363.81(16) A , Z = 2, q = 1.622 g/cm . 17,936 Reflections
were measured. An analytical absorption correction was
applied (l = 5.57 mmꢀ1
, 0.38–0.66 correction range).
3
(D2O, 300 MHz): d = 7.73 (dd, 6H, JHH = 8.1 Hz,
3
3JPH = 12.9 Hz, ArH), 7.66 (dd, 6H, JHH = 8.1 Hz,
2088 Reflections were unique (Rint = 0.037). 102 Parame-
ters were refined with one restraint. R1/wR2 [I > 2r(I)]:
0.0139/0.0280. R1/wR2 [all reflections]: 0.0181/0.0289.
4JPH = 2.1 Hz, ArH), 4.42 (s, 6H, CH2N), 2.89 (s, 18H,
N(CH3)2); 13C NMR (D2O, 75 MHz): d = 135.21 (d,

432
R. Kreiter et al. / Journal of Organometallic Chemistry 691 (2006) 422–432
[4] See for example: (a) S.D. Walker, T.E. Barder, J.R. Martinelli, S.L.
Buchwald, Angew. Chem., Int. Ed. 43 (2004) 1871;
S = 1.084. Flack parameter x = ꢀ0.026(6). Residual elec-
3
˚
tron density between ꢀ0.26 and 0.76 e/A .
(b) O. Niyomura, M. Tokunaga, Y. Obora, T. Iwasawa, Y. Tsuji,
Angew. Chem., Int. Ed. 42 (2003) 1287.
6. Supplementary materials
´
[5] See for example: (a) M. Aranza Alonso, J.A. Casares, P. Espinet, K.
Soulantica, Inorg. Chem. 42 (2003) 3856;
(b) V.F. Slagt, J.N.H. Reek, P.C.J. Kamer, P.W.N.M. van Leeuwen,
Angew. Chem., Int. Ed. 40 (2001) 4271;
(c) B. Breit, W. Sache, Angew. Chem., Int. Ed. 44 (2005) 1640;
(d) N.C. Gianneschi, S.T. Nguyen, C.A. Mirkin, J. Am. Chem. Soc.
127 (2005) 1644.
CCDC-274165 (compound 8) and 274166 (12) contain
the supplementary crystallographic data for this paper.
These data can be obtained free of charge via www.ccdc.
cam.ac.uk/conts/retrieving.html (or from the CCDC, 12
Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223
336033; e-mail: deposit@ccdc.cam.ac.uk).
[6] D.A. Atwood, A.H. Cowley, J. Ruiz, Inorg. Chim. Acta 198-200
(1992) 271.
´
´
[7] F. Carre, C. Chuit, R.J.P. Corriu, A. Mehdi, C. Reye, J. Organomet.
Chem. 529 (1997) 59.
Note added in proof
[8] R. Kreiter, R.J.M. Klein Gebbink, G. van Koten, Tetrahedron 59
(2003) 3389.
[9] P. Steenwinkel, S.L. Stuart James, D.M. Grove, N. Veldman, A.L.
Spek, G. van Koten, Chem. Eur. J. 2 (1996) 1440.
[10] M. Albrecht, G. van Koten, Angew. Chem., Int. Ed. 40 (2001)
3750.
[11] I.M. Al-Naiiar, Inorg. Chim. Acta 128 (1987) 93.
[12] Crystal structure of ClAuPPh3 from CCDB (CTPPAU); Fit achieved
by removal of the CH2N(CH3)2 fragments from complex 8, and use of
the fit by click routine in PLATON [22].
Recently, single crystals were obtained for complex 13,
which turned out to be the trans isomer. Full details of
the structure of trans-13 and on its structural analysis will
be submitted shortly to Acta Crystallographica.
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