Tris(mercaptoimidazolyl)borate complexes of the coinage metals: Syntheses and molecular structures of the first gold compounds and related copper and silver derivatives

Article abstract of DOI:10.1039/b506046j

The first tris(mercaptoimidazolyl)borate complexes of gold, Au(Tm ^tBu) and (Tm^tBu)Au(PPh₃), have been prepared and structurally characterized. Together with their copper and silver analogues M(Tm^tBu) and (Tm

Full text of DOI:10.1039/b506046j

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F U L L P A P E R
Tris(mercaptoimidazolyl)borate complexes of the coinage metals:
syntheses and molecular structures of the first gold compounds and
related copper and silver derivatives
a
a
b
b
c
Denish V. Patel, David J. Mihalcik, Kevin A. Kreisel, Glenn P. A. Yap, Lev N. Zakharov,
c
c
a
W. Scott Kassel,† Arnold L. Rheingold and Daniel Rabinovich*
a
Department of Chemistry, The University of North Carolina at Charlotte, 9201 University
City Boulevard, Charlotte, North Carolina, 28223, USA. E-mail: drabinov@email.uncc.edu
Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware,
b
c
19716, USA
Department of Chemistry and Biochemistry, University of California-San Diego, 9500 Gilman
Drive, La Jolla, California, 92093, USA
Received 29th April 2005, Accepted 27th May 2005
First published as an Advance Article on the web 13th June 2005
tBu
tBu
The first tris(mercaptoimidazolyl)borate complexes of gold, Au(Tm ) and (Tm )Au(PPh ), have been prepared and
3
tBu
tBu
structurally characterized. Together with their copper and silver analogues M(Tm ) and (Tm )M(PPh
3
) (M = Cu,
R
Ag), these compounds constitute the first two complete series of Tm derivatives to be isolated for the coinage metals.
In order to evaluate the steric and electronic effects of the bulky tert-butyl substituents in these species, comparative
Me
Me
structural analyses with the known methyl-substituted analogue Ag(Tm ) and various (Tm )M(PR
3
) derivatives
(
M = Cu, Ag) are also presented.
Introduction
ranges from the preparation of several well-defined sulfur-
4 5
rich complexes of cobalt and the group 12 metals to the
The tris(2-mercapto-1-tert-butylimidazolyl)borate ligand (Fig. 1)
is quickly becoming one of the most conspicuous members
of the tris(mercaptoimidazolyl)borate (Tm ) family of ligands.
Developed independently by the Vahrenkamp and Rabinovich
groups, alkali metal salts of [Tm ] can be readily prepared in
high yield and its complexes usually display good solubility, sim-
ple spectroscopic (e.g., NMR) features in solution and good crys-
R
6
syntheses of the first organobismuth Tm compound and the
7
first hydroselenido derivative of zinc. We have now extended
R
1
these studies to the coinage metals and report in this paper the
2
3
R
first two complete series of Tm derivatives of these elements,
tBu
−
including the first such complexes of gold to be synthesized
and structurally characterized. Although the silver complex
Me
Ag(Tm ) and a number of tertiary phosphine derivatives
tBu
−
tallinity in the solid state. The coordination chemistry of [Tm
]
Me
(
Tm )M(PR
3
) (M = Cu, Ag; R = alkyl, aryl) have been reported
8
in recent years, these species are all circumscribed to the original
Me
−
1
†
Permanent address: Department of Chemistry, Villanova University,
[Tm ] ligand, and our studies are thus also aimed at assessing
the effect on bonding and structure of the bulkier borate ligand
Villanova, Pennsylvania 19085, USA.
tBu
tBu
present in M(Tm ) and (Tm )M(PPh
3
) (M = Cu, Ag, Au).
Results and discussion
tBu
Synthesis and structures of (Tm )M(PPh
3
) (M = Cu, Ag)
tBu
The tris(mercaptoimidazolyl)borate complexes (Tm )M(PPh )
3
(
M = Cu, Ag) were easily prepared by allowing equimo-
lar amounts of sodium tris(2-mercapto-1-tert-butylimidazolyl)-
borate, triphenylphosphine, and either copper(I) chloride or
silver(I) nitrate to react in methanol (Scheme 1). The white,
air- and light-stable products were isolated in ca. 75% yield
after the appropriate work-up and are moderately soluble in
chlorinated hydrocarbons (e.g., CH
2
Cl
2
, CHCl ) but essentially
3
Fig.
1
The tris(2-mercapto-1-tert-butylimidazolyl)borate ligand,
insoluble in other common organic solvents such as acetone,
acetonitrile or benzene. They were characterized analytically
tBu
−
[
Tm ] .
Scheme 1
T h i s j o u r n a l i s © T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 5
2
4 1 0
D a l t o n T r a n s . , 2 0 0 5 , 2 4 1 0 – 2 4 1 6

View Online
1
13
and spectroscopically, including H and C NMR and IR
spectroscopies, and all the data are consistent with the presence
of mononuclear pseudo-tetrahedral species both in solution and
the metal and phosphorus atoms. As such, they resemble
Me 8d
Pettinari and Santini’s (Tm )Cu(PAr
3
) (Ar = m-tolyl, p-tolyl)
complexes and display comparable
metrical parameters. For example, the M–S bond lengths in
Me
i
8e
and (Tm )Ag(PBu )
3
in the solid state.
tBu
tBu
˚
˚
The molecular structures of both (Tm )M(PPh
Cu, Ag) were confirmed by single-crystal X-ray diffraction
Figs. 2–3) and selected bond lengths (A) and angles ( ) are
included in Table 1. The complexes are isostructural and
present slightly distorted tetrahedral geometries, with crys-
tallographically imposed three-fold rotation axes containing
3
) (M =
(Tm )M(PPh
3
) [2.353(1) A for M = Cu, 2.590(1) A for M =
Me
Ag] are virtually identical to those in (Tm )Cu(PAr
3
) [2.357(2)
◦
˚
˚
(
and 2.332(1) A for Ar = m-tolyl and p-tolyl, respectively] and in
Me i
3
˚
(Tm )Ag(PBu ) [2.595(1) A]. Similarly, the M–P bond lengths
tBu
˚
˚
in (Tm )M(PPh
Ag] do not differ significantly from the corresponding values
found in (Tm )Cu(PAr
tolyl and p-tolyl, respectively] or in (Tm )Ag(PBu ) [2.404(1)
A]. Although the S–M–S angles in all these complexes are
consistently smaller (and the S–M–P angles are consistently
larger) than the ideal tetrahedral values, they tend to deviate
more so in the silver complexes (by ca. 9–12 ) than in the copper
derivatives (by ca. 2–5 ). It is also worth noting that the distorted
3
) [2.221(1) A for M = Cu, 2.424(1) A for M =
Me
˚
3
) [2.217(3) and 2.226(1) A for Ar = m-
Me
i
3
˚
◦
◦
tetrahedral silver atom in the related tricyclohexylphosphine
Me
8b
complex (Tm )Ag(PCy
3
)
exhibits a distinctively different
coordination environment, with a weak Ag · · · H–B interaction
supplementing the binding of the phosphine and only two of the
Me
−
three thione groups of the [Tm ] ligand to the metal center.
tBu
Me
i
Since (Tm )Ag(PPh
3
) and (Tm )Ag(PBu ) have very similar
3
3
structures, the j -S,S,H coordination mode observed for the
Me
borate ligand in (Tm )Ag(PCy
of the larger cone angle of PCy
3
) is likely to be a consequence
◦
3
(170 ) relative to those of either
◦
i
◦
9
PPh
3
(145 ) or PBu (143 ).
3
tBu
Homoleptic M(Tm ) complexes (M = Cu, Ag)
The base-free tris(mercaptoimidazolyl)borate
tBu
3
Fig. 2 Molecular structure of (Tm )Cu(PPh ). Thermal ellipsoids are
com-
depicted at the 30% probability level and hydrogen atoms (except for the
one directly attached to boron) are omitted for clarity. The equivalent
positions (1 − y, x − y, z) and (1 − x + y, 1 − x, z) are indicated in the
atomic labels by the use of the additional letters “A” and “B”.
tBu
plexes M(Tm ) (M = Cu, Ag) were similarly obtained
from the reaction of equimolar methanolic solutions
tBu
of Na(Tm ) and copper(I) chloride or silver(I) nitrate,
respectively, and were isolated in 75–80% yield as white air- and
light-stable solids. Unlike the triphenylphosphine derivatives
tBu
(
Tm )M(PPh ) described above, they are both soluble in
3
acetone, benzene and dimethyl sulfoxide (DMSO) in addition to
chlorinated hydrocarbons. The observation of virtually identical
spectroscopic (e.g., NMR and IR) and physical properties for
both compounds suggests that their structures, both in solution
and in the solid state, are probably very similar.
tBu
The molecular structure of Ag(Tm ) was established by
single-crystal X-ray diffraction (Fig. 4) and selected bond
◦
˚
lengths (A) and angles ( ) are shown in Table 2. Each of the
two silver atoms in the centrosymmetric dimer is in a distorted
tetrahedral environment, coordinated by two thione groups from
tBu
−
each of the two [Tm
] ligands, which also partake in weak
Ag · · · H–B interactions with the metal centers (Fig. 5).
tBu
While the overall structure of Ag(Tm ) is similar to that
Me 8c
of the methyl-substituted analogue Ag(Tm ), including the
presence of a planar [Ag
coordination mode (l-j -S,S:j -S,S) exhibited by the borate
ligands, there are some significant differences as well. For
example, whereas the angles subtended at silver in Ag(Tm
are in the approximate range 90–126 , those in Ag(Tm ) deviate
less from the ideal tetrahedral value (ca. 101–122 ). The central
2
S ] core and the bridging bis(bidentate)
2
tBu
2 2
Fig. 3 Molecular structure of (Tm )Ag(PPh
3
). Thermal ellipsoids are
depicted at the 30% probability level. Hydrogen atoms (except for the
one directly attached to boron) and solvent molecules are omitted for
clarity. The equivalent positions (1 − y, x − y, z) and (1 − x + y, 1 − x,
z) are indicated in the atomic labels by the use of the additional letters
tBu
)
◦
Me
◦
“A” and “B”.
tBu
[
Ag
2
S ] parallelogram in Ag(Tm ) is somewhat more elongated
Me
2
◦
tBu
than that in Ag(Tm ), with slightly more acute Ag–S–Ag and
Table 1 Selected bond lengths ( A˚ ) and angles ( ) for (Tm )M(PPh
M = Cu, Ag)
)
3
(
◦
tBu
Table 2 Selected bond lengths ( A˚ ) and angles ( ) for Ag(Tm
)
M = Cu
M = Ag
Ag(1)–S(1)
Ag(1)–S(1A)
Ag(1)–S(2)
Ag(1)–S(3A)
2.5952(6)
2.8419(6)
2.5492(7)
2.5691(6)
Ag(1) · · · Ag(1A)
S(1)–C(1)
S(2)–C(8)
3.1578(4)
1.715(2)
1.710(2)
1.707(3)
M–S
M–P
S–C
2.3534(7)
2.2214(14)
1.707(3)
2.5896(7)
2.4239(12)
1.709(3)
S(3)–C(15)
S–M–S
S–M–P
M–S–C
M–P–C
104.56(2)
114.02(2)
99.78(9)
97.32(2)
S(1)–Ag(1)–S(1A)
S(1)–Ag(1)– S(3A)
S(1A)–Ag(1)–S(3A) 105.21(2)
Ag(1)–S(1)–Ag(1A) 70.847(16)
109.153(16) S(1)–Ag(1)–S(2)
111.44(2) S(1A)–Ag(1)–S(2)
126.09(2)
89.80(2)
119.894(17)
100.14(10)
114.90(10)
S(2)–Ag(1)–S(3A) 111.07(2)
115.04(10)
D a l t o n T r a n s . , 2 0 0 5 , 2 4 1 0 – 2 4 1 6
2 4 1 1

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tBu
tBu
Synthesis and structures of (Tm )Au(PPh
3
) and Au(Tm
complexes
) and Au(Tm ) were cleanly synthesized
)
The
gold(I)
tris(mercaptoimidazolyl)borate
tBu
tBu
(
Tm )Au(PPh
3
tBu
from Na(Tm ) and commercially available (PPh
the well-known tetrahydrothiophene adduct (tht)AuCl,
3
)AuCl or
11
respectively, and isolated in 85–90% yield (Scheme 2). The
off-white air-stable solids are not particularly sensitive to
light and they are fairly soluble in unsaturated hydrocarbons
(
e.g., benzene, toluene) as well as in more polar organic
solvents, including acetone, acetonitrile and dichloromethane.
tBu
In addition, the homoleptic gold complex Au(Tm ) is also
soluble in ethereal solvents such as tetrahydrofuran (THF) and
tBu
tBu
diethyl ether. Significantly, (Tm )Au(PPh ) and Au(Tm )
3
are the first gold tris(mercaptoimidazolyl)borate complexes
to be reported and, together with their copper and silver
R
analogues, they constitute the first two complete series of Tm
12
derivatives to be isolated for the coinage metals. It is also worth
noting that the preparation of the related tris(pyrazolyl)borate
t
12c
derivatives (Tp)Au(PR
3
) and (Tp*)Au(PR
3
) (R = Bu , Ph)
requires the use of an excess of the phosphines to inhibit the
formation of decomposition products, a situation that we have
not encountered in the synthesis of our gold(I) complexes.
tBu
Fig. 4 Molecular structure of Ag(Tm ). Thermal ellipsoids are
depicted at the 30% probability level. Hydrogen atoms (except for those
directly attached to boron) and solvent molecules are omitted for clarity.
The equivalent positions (2 − x, 1 − y, 1 − z) are indicated in the atomic
labels by the use of the additional letter “A”.
Scheme 2
tBu
tBu
Both (Tm )Au(PPh ) and Au(Tm ) have been characterized
3
by a combination of analytical and spectroscopic techniques,
including elemental analysis (CHN) and NMR and IR spec-
troscopies. Interestingly, the H and C NMR spectra of
tBu
Fig. 5 Schematic representation of dimeric [Ag(Tm )]
2
.
1
13
tBu
(
Tm )Au(PPh
3
) obtained in CDCl show only one set of
3
tBu
−
slightly more obtuse S–Ag–S internal angles being observed in
the former. Both observations suggest that the bulkier tert-butyl-
substituted ligand present in Ag(Tm ) does exert a tangible
albeit modest steric effect on the overall structure of the complex.
resonances for the [Tm ] ligands, an observation that suggests
the existence in solution of a nearly tetrahedral species or, alter-
natively, a highly fluxional molecule of lower average symmetry
(vide infra). In this regard, we note that there are no significant
tBu
R
t
1
tBu
The two [Ag(Tm )]
2
compounds (R = Me, Bu ) exhibit three
differences in the H NMR spectra of (Tm )Au(PPh
3
) in
◦
˚
“
normal” Ag–S bond distances (2.524–2.595 A), values which
CD
2
Cl
2
collected between room temperature and −90 C. The
R
tBu
are similar to those in the (Tm )Ag(PR’
3
) derivatives described
above and are only marginally longer than the mean value
2.514 A) found for such interactions in a variety of thione
complexes of silver, as listed in the Cambridge Structural
Database (CSD). However, each of the two complexes also
displays a significantly longer Ag–S bond length involving one
of the two bridging thione groups (ca. 2.85 A), distance which
fluxionality of Au(Tm ) in solution is also apparent from the
observation of only one broad resonance for the two imidazole
ring protons (d 6.84 ppm) as well as a single peak for the tert-
˚
(
1
butyl groups (d 1.80 ppm) in its H NMR spectrum.
10
Since gold compounds in the +1 oxidation state have a
marked preference for linear coordination, with three- and
13
˚
four-coordinate species being clearly less common, we set out
to grow single crystals amenable to X-ray diffraction studies
lies outside the range found in the CSD for such fragments
tBu
tBu
˚
(
2.395–2.708 A). In the same vein, the Ag · · · H–B interactions
for both (Tm )Au(PPh ) and Au(Tm ) in order to elucidate
3
tBu
˚
observed in Ag(Tm ) (2.52 and 2.66 A), while comparable to
their structures unambiguously, at least in the solid state.
After numerous crystallization attempts, suitable crystals were
finally obtained by slow diffusion of pentane into benzene or
Me
˚
those reported for Ag(Tm ) (2.45 and 2.83 A), are longer than
most of the relevant values listed in the CSD, in the range 1.76–
10
˚
˚
2
.57 A (mean = 2.11 A).
toluene solutions of the complexes. The molecular structure
tBu
In preliminary reactivity studies, we have found that
of (Tm )Au(PPh ) is shown in Fig. 6, with selected bond
3
tBu
Ag(Tm ) is a viable ligand-transfer reagent, particularly for
lengths and angles for the four independent but chemically
tBu
the syntheses of complexes where the use of Na(Tm ) is not
identical molecules found in the unit cell listed in Table 3.
tBu
effective and the application of the more toxic thallium derivative
Tl(Tm ) has been prescribed. Thus, the cobalt(II) complex
Tm )CoBr can be prepared in ca. 65% yield and spectroscop-
ically pure form starting from anhydrous CoBr and Tl(Tm ).
Much like in the metathesis reactions between transition metal
halide or alkyl complexes and the thallium reagent, those with
Ag(Tm ) are driven by the formation of insoluble silver(I)
halides or the decomposition of the thermodynamically unstable
silver(I) alkyl by-products, respectively.
Unlike its lighter analogues (Tm )M(PPh
3
) (M = Cu, Ag) or
tBu
the pseudo-tetrahedral tris(3,5-dimethylpyrazolyl)borate com-
tBu
4
12c
(
plex (Tp*)Au(PPh
3
), the new mononuclear complex displays
tBu
2
a distorted trigonal planar (“T-shape”) geometry, with the
tBu
−
phosphine and two of the thione groups of the [Tm ] ligand
coordinating to the metal center. As such, it closely resembles the
structure of the related bis(mercaptoimidazolyl)borate complex
tBu
Me
14
(Bm )Au(PPh
3
), including the presence of a weak Au · · · H–
B interaction roughly perpendicular to the [AuS P] plane, but
2
2
4 1 2
D a l t o n T r a n s . , 2 0 0 5 , 2 4 1 0 – 2 4 1 6

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◦
tBu
Table 3 Selected bond lengths ( A˚ ) and angles ( ) for the four independent molecules present in the unit cell of (Tm )Au(PPh
)
3
Molecule A
Molecule B
Molecule C
Molecule D
Au(1)–S(1)
Au(1)–S(2)
Au(1)–P(1)
S(1)–C(1)
S(2)–C(7)
S(3)–C(4)
2.3488(11)
2.8291(14)
2.2535(11)
1.732(5)
1.702(4)
1.688(4)
2.3488(11)
2.8455(14)
2.2474(11)
1.721(5)
1.699(5)
1.681(4)
2.3400(11)
2.8352(11)
2.2492(11)
1.725(4)
1.694(4)
1.696(4)
2.3442(11)
2.8441(12)
2.2492(11)
1.730(4)
1.698(4)
1.688(4)
S(1)–Au(1)–S(2)
S(1)–Au(1)–P(1)
S(2)–Au(1)–P(1)
96.88(4)
160.56(5)
101.94(5)
96.91(4)
159.30(5)
102.98(5)
102.43(4)
159.47(4)
96.69(4)
100.87(4)
159.75(4)
97.21(4)
◦
tBu
Table 4 Selected bond lengths ( A˚ ) and angles ( ) for Au(Tm
)
Au(1)–S(1)
Au(1)–S(6)
2.291(2) Au(2)–S(3)
2.295(2) Au(2)–S(4)
2.291(2)
2.299(2)
3.38
Au(1) · · · H(1)
2.96
2.96
Au(2) · · · H(1)
Au(1) · · · H(2)
Au(2) · · · H(2)
3.27
S(1)–Au(1)–S(6)
173.51(7) S(3)–Au(2)–S(4)
176.94(8)
58.9
123.3
123.7
59.4
S(1)–Au(1) · · · H(1)
S(1)–Au(1) · · · H(2)
S(6)–Au(1) · · · H(1)
S(6)–Au(1) · · · H(2)
70.7
108.4
114.0
75.6
S(3)–Au(2) · · · H(1)
S(3)–Au(2) · · · H(2)
S(4)–Au(2) · · · H(1)
S(4)–Au(2) · · · H(2)
H(1) · · · Au(2) · · · H(2)
H(1) · · · Au(1) · · · H(2) 101.5
87.4
tBu
The molecular structure of Au(Tm ) (Fig. 7, Table 4) also
proved to be quite different from that of its silver analogue
described above. The dinuclear complex displays a novel twisted
1
6-membered ring structure reminiscent of a bow-tie or a
Fig. 6 Molecular structure of one of the four independent but
18
tBu
Lissajous curve (Fig. 8), with each gold center coordinated by
a single thione group from a [Tm ] ligand in an approximate
3
chemically identical molecules found in the unit cell of (Tm )Au(PPh ).
tBu
−
Thermal ellipsoids are depicted at the 30% probability level. Hydrogen
atoms (except for the one directly attached to boron) and solvent
molecules are omitted for clarity.
◦
linear fashion (S–Au–S ≈ 173.5 and 176.9 ). Significantly,
1
1
the bridging bis(monodentate) coordination mode (l-j -S:j -
tBu
S) exhibited by the two borate ligands in [Au(Tm )] is un-
precedented in Tm chemistry, even though both monodentate
2
R
with the third mercaptoimidazolyl group not coordinated to
the metal. Accordingly, we note that: (i) the sum of angles
◦
subtended at the gold center is approximately 358.7 , (ii) the
◦
average S(1)–Au(1)–P(1) angle is 159.8 , and (iii) all the S(1)–
Au–S(2) and S(2)–Au(1)–P(1) angles are in the relatively nar-
◦
row range 96.7–103.0 . In addition, the degree of structural
distortion from the ideal T-shape and regular trigonal planar
geometries in this and other three-coordinate complexes could
ꢀ
be estimated using a modified trigonality index s = (b −
◦
a)/90 we introduce herein, where b and a are the largest
15
and second-largest interligand angles. Thus, the value of
ꢀ
tBu
s = 0.64 calculated for (Tm )Au(PPh
3
) is consistent with
ꢀ
a distorted geometry in between the ideal T-shape (s = 1)
ꢀ
tBu
−
and trigonal planar (s = 0) options. The [Tm
] ligand in
tBu
(
Tm )Au(PPh ) exhibits a severely asymmetric bidentate (i.e.,
3
2
anisobidentate) j -S,S coordination mode, with the two Au–
S bond lengths differing by almost 0.50 A, much like in the
structure of (Bm )Au(PPh
More specifically, whereas the “short” Au–S bond lengths
˚
Me
14
˚
3
) mentioned above (Dd = 0.46 A).
tBu
Fig. 7 Molecular structure of Au(Tm ). Thermal ellipsoids are
depicted at 30% probability. Hydrogen atoms (except for those directly
attached to boron) and solvent molecules are omitted for clarity.
˚
(
average for the four independent molecules = 2.345 A) are
only slightly longer than the corresponding values found in a
variety of thiourea and heterocyclic thione complexes of gold(I),
16
˚
all of which are in the relatively narrow range 2.25–2.33 A,
˚
the “long” Au–S bond lengths (average = 2.838 A) are clearly
outside the norm. Despite the disparity in Au–S bond lengths,
˚
the Au–P bond distance (average = 2.250 A) is very close to
the mean value found in the CSD for three-coordinate gold
10
˚
phosphine complexes (2.295 A). With regards to the Au · · · H
tBu
˚
bond distances in (Tm )Au(PPh
3
) (average = 2.47 A), they
are significantly weaker (i.e., longer) than those in the only
three compounds listed in the CSD that display such Au · · · H–
Fig. 8 Schematic representation of the 16-membered ring in the
tBu
2
molecular structure of [Au(Tm )] and (to the right) a prototypical
17
˚
B interactions (1.80–1.91 A) and appear to have a negligible
effect on the overall structure of the complexes.
two-dimensional Lissajous curve described by the parametric equations
x(t) = Asin(t + p/2) and y(t) = Bsin(2t).
D a l t o n T r a n s . , 2 0 0 5 , 2 4 1 0 – 2 4 1 6
2 4 1 3

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1
1
1
1
(
j -S) and tris(monodentate) (l-j -S:j -S:j -S) coordination
45 min, a small amount of water (1 mL) was added to the reaction
modes have been previously identified in the main-group
mixture and the product was isolated by filtration, washed with
water (5 mL), and dried in vacuo for 18 h (0.118 g, 74%). Mp 248–
Me
19
metal complexes (Tm )SnR
3
(R = Ph, cyclohexyl) and
tBu
+
6
◦
1
[
(Me
in [Au(Tm )]
the three-dimensional loop structure, their separation (Au · · · Au
2
Bi)
3
(Tm
)
2
] , respectively. Although the two gold atoms
251 C. NMR data (in CDCl
3
): H d 1.58 [s, 27H, C(CH
3
) ], 6.69
3
tBu
3
2
are roughly facing each other halfway through
[br s, 3H, imidazole H], 6.79 [d, JH–H = 2.1, 3H, imidazole H],
7.26 (br s, 6H, C
6
H
5
), 7.46 (br s, 9H, C
C d 28.7 [q, JC–H = 127, 9C, C(CH
114.7 [dd, JC–H = 192, JC–H = 12, 3C, imidazole C], 122.5 [br d,
6
H
5
), BH not observed;
20
13
1
˚
≈
4.266 A) precludes the existence of an aurophilic interaction
3
)
3
], 58.3 [s, 3C, C(CH ],
)
3 3
1
2
between them. The four unique Au–S bond lengths present in
tBu
1
1
3
˚
[
Au(Tm )]
2
are almost identical (2.291–2.299 A) and fall within
J
C–H = 195, 3C, imidazole C], 128.1 [dd, JC–H = 161, JP–C = 9,
1
1
˚
the range of values (2.25–2.33 A) observed for such moieties in
thione complexes of gold(I), as mentioned above.
6C, C
m
], 128.8 [d, JC–H = 160, 3C, C
p
], 134.0 [dd, JC–H = 162,
2
J
P–C = 16, 6C, C ], 161.4 [s, 3 C, C = S], Cipso not observed. IR
o
data: 3186 (w), 3155 (w), 3047 (w), 2963 (w), 2921 (w), 2369 (w),
292 (w), 2225 (w), 1645 (w), 1571 (w), 1539 (w), 1480 (w), 1435
m), 1413 (m), 1394 (m), 1360 (s), 1291 (w), 1259 (w), 1222 (m),
2
(
Conclusions
tBu
The six tris(mercaptoimidazolyl)borate complexes (Tm )-
1197 (s), 1175 (m), 1134 (w), 1094 (w), 1069 (w), 1029 (w), 928
(w), 821 (w), 760 (w), 743 (w), 718 (m), 692 (m), 682 (m), 591
(w), 558 (w), 519 (m), 497 (m), 458 (w), 431 (w). Anal. Calc. for
C H BCuN PS : C, 58.3; H, 6.2; N, 10.5. Found: C, 58.6; H,
tBu
M(PPh
3
) and M(Tm ) (M = Cu, Ag, Au) comprise the first
R
two complete series of Tm derivatives to be isolated for the
coinage metals. Single-crystal X-ray diffraction studies have
confirmed that whereas the triphenylphosphine derivatives are
mononuclear in the solid state, the homoleptic compounds
3
9
49
6
3
6.2; N, 10.4%.
tBu
tBu
tBu
are dimeric. Significantly, (Tm )Au(PPh
3
) and Au(Tm ) are
3. Synthesis of (Tm )Ag(PPh
3
)
R
the first two Tm complexes of gold to be synthesized and
structurally characterized and their structures have uncovered
two new coordination modes for this ligand system: asymmetric
bidentate (i.e., anisobidentate) in the former and bridging
bis(monodentate) in the latter. Our studies suggest that the
presence of bulky tert-butyl substituents in the mercaptoim-
idazolyl rings tends to improve the solubility, stability, and
Methanol (10 mL) was added to a mixture of AgNO
0
3
(0.117 g,
.600 mmol), Na(Tm ) (0.300 g, 0.600 mmol), and triph-
tBu
enylphosphine (0.157 g, 0.599 mmol), resulting in the formation
of a white suspension within 5 min. After stirring for 45 min,
a small amount of water (1 mL) was added to the reaction
mixture and the product was isolated by filtration, washed with
water (5 mL), and dried in vacuo for 18 h (0.375 g, 74%). Mp
tBu
−
crystallinity of [Tm ] complexes relative to those derived from
◦
1
2
2
35–238 C (decomp.). NMR data (in CDCl
7H, C(CH ], 6.56 [br s, 3 H, imidazole H], 6.80 [br s, 3 H,
), 7.49 (br s, 9 H, C ), BH
not observed; C d 28.6 [q, JC–H = 128, 9C, C(CH ], 58.3 [s, 3
C, C(CH
3
): H d 1.74 [s,
Me
−
[
Tm ] . However, the steric effect of the ring substituents on the
3 3
)
overall structures and geometries of these types of complexes
appears to be modest at best since analogous species such as
imidazole H], 7.31 (br s, 6 H, C
6
H
5
6
H
5
13
1
3 3
)
R
R
t
Ag(Tm ) and (Tm )M(PR
3
) (M = Cu, Ag) (R = Me, Bu ) exhibit
1
2
3
)
3
], 114.7 [dd, JC–H = 193, JC–H = 11, 3C, imidazole
comparable metrical parameters. This is in contrast to the related
tris(pyrazolyl)borate family of ligands, for which the use of tert-
butyl groups in the 3-position of the pyrazolyl rings has a pro-
found effect on structure and reactivity and has earned ligands
1
1
C), 119.9 [d, JC–H = 192, 3 C, imidazole C], 128.5 [dd, JC–H
=
3
1
1
61, JP–C = 7, 6 C, C
m
], 129.5 [d, JC–H = 160, 3 C, C
p
], 134.1 [dd,
1
2
J
C–H = 162, JP–C = 17, 6 C, C
o
], 161.0 [s, 3 C, C=S], Cipso not
observed. IR data: 3175 (w), 3144 (w), 3054 (w), 2953 (m), 2919
tBu
−
21
such as [Tp ] the reputation of “tetrahedral enforcers”.
(
1
m), 2381 (w), 2289 (w), 2233 (w), 1667 (w), 1586 (w), 1572 (w),
479 (w), 1435 (m), 1412 (m), 1393 (m), 1353 (vs), 1294 (w), 1259
(w), 1221 (w), 1194 (s), 1173 (m), 1095 (w), 1066 (w), 1028 (w),
25 (w), 822 (w), 759 (w), 745 (m), 723 (w), 695 (m), 684 (w), 589
w), 555 (w), 517 (m), 496 (m). Anal. Calc. for C39 PS :
Experimental
9
(
1. General considerations
H
49AgBN
6
3
All reactions were performed under aerobic conditions un-
less otherwise noted, solvents were purified and degassed by
standard procedures, and all commercially available reagents,
C, 55.3; H, 5.8; N, 9.9. Found: C, 54.8; H, 5.8; N, 9.6%.
tBu
4
.
Synthesis of (Tm )Au(PPh )
3
including (Ph
3
P)AuCl (Aldrich), were used as received. Whereas
tBu
Methanol (15 mL) was added to a mixture of Na(Tm ) (0.202 g,
.404 mmol) and (Ph P)AuCl (0.200 g, 0.404 mmol), resulting in
tBu
3
Na(Tm ) was prepared as reported, the tetrahydrothiophene
adduct (tht)AuCl was synthesized following a modified literature
0
3
immediate formation of a brown solution and, within 5 min, an
off-white precipitate. After stirring the suspension for 1 h and
adding a small amount of water (ca. 2 mL), the product was
isolated by filtration, washed with water (5 mL) and dried in
11
procedure, starting from gold shot (99.99%, David H. Fell &
Company, Inc.), which was dissolved in aqua regia [i.e., a 3 : 1
mixture (v/v) of concentrated hydrochloric and nitric acids) to
1
13
generate an aqueous solution of HAuCl
spectra were obtained on Varian Gemini (300 MHz) or JEOL
ECA-500 (500 MHz) FT spectrometers. Chemical shifts are
4
. H and C NMR
◦
vacuo for 16 h (0.321 g, 85%). Mp 222–224 C (decomp.). NMR
1
data (in CDCl
6
3
): H d 1.72 [s, 27H, C(CH
3
) ], 6.07 [br s, 1H, BH],
3
3
3
.73 [d, JH–H = 2.4, 3 H, imidazole H], 6.79 [d, JH–H = 2.4, 3H,
imidazole H], 7.39 [br s, 9H, C ], 7.57 [m, 6H, C ]; C d
], 58.2 [s, 3C, C(CH ], 114.7
1
13
reported in ppm relative to SiMe
4
(d = 0 ppm) for H and C and
13
6
H
5
6
H
5
were referenced internally with respect to the solvent resonances
1
2
[
1
1
6
8.7 [q, JC–H = 127, 9C, C(CH
3
)
3
)
3 3
1
13
(
H: d 7.24 for CHCl
3
; C: d 77.0 for CDCl
3
); coupling constants
1
2
1
dd, JC–H = 193, JC–H = 12, 3C, imidazole C], 121.6 [dd, JC–H
=
are given in hertz (Hz). IR spectra were recorded as KBr pellets
on a Thermo Mattson Satellite 3000 FT-IR spectrophotometer
and are reported in cm ; relative intensities of the absorptions
are indicated in parentheses (vs = very strong, s = strong, m =
medium, w = weak). Elemental analyses were determined by
Atlantic Microlab, Inc. (Norcross, GA).
2
1
3
94, JC–H = 10, 3C, imidazole C], 128.8 [d, JC–H = 161, JPvC
1, 6C, C ], 130.9 [s, 3C, C
C, C
=
1
2
m
p
], 134.5 [d, JC–H = 162, JP–C = 14,
−
1
], 159.3 [s, 3C, C=S], Cipso not observed. IR data: 3154
o
(
1
w), 3051 (w), 2974 (m), 2921 (w), 2411 (w), 1560 (w), 1479 (w),
435 (m), 1397 (m), 1359 (s), 1304 (w), 1259 (m), 1199 (m), 1165
m), 1099 (m), 821 (w), 750 (w), 708 (w), 694 (m), 535 (m), 510
(
(
w). Anal. Calc. for C39
H
49AuBN
6
PS
3
: C, 50.0; H, 5.3; N, 9.0.
tBu
2
.
Synthesis of (Tm )Cu(PPh )
3
Found: C, 49.8; H, 5.3; N, 8.8%.
Methanol (8 mL) was added to a mixture of copper(I) chloride
tBu
5
. Synthesis of Cu(Tm )
tBu
(
0.020 g, 0.202 mmol), Na(Tm ) (0.100 g, 0.200 mmol), and
tBu
triphenylphosphine (0.052 g, 0.198 mmol), resulting in the
immediate formation of a white suspension. After stirring for
Methanol (10 mL) was added to a mixture of Na(Tm ) (0.200 g,
0.400 mmol) and copper(I) chloride (0.040 g, 0.404 mmol),
2
4 1 4
D a l t o n T r a n s . , 2 0 0 5 , 2 4 1 0 – 2 4 1 6

View Online
1
1
resulting in the formation of a slightly cloudy solution. After
stirring for 1 h, the solution was filtered and the filtrate was
concentrated under reduced pressure to ca. 2 mL. Addition of
water (5 mL) resulted in the separation of the white solid, which
was isolated by filtration and dried in vacuo for 18 h (0.168,
J
C–H = 127, 9C, C(CH
3
)
3
], 59.1 [s, 3C, C(CH
3
)
3
], 115.7 [d, JC–H
=
1
195, 3C, imidazole C], 124.0 [d, JC–H = 196, 3C, imidazole C],
150.7 [s, 3C, C=S]. IR data: 3146 (w), 2975 (m), 2923 (w), 1655
(w), 1560 (w), 1480 (w), 1419 (w), 1398 (m), 1355 (s), 1303 (w),
1263 (w), 1200 (m), 1160 (m), 1102 (m), 1058 (w), 1002 (w), 982
◦
1
78%). Mp 207–209 C. NMR data (in CDCl
3
): H d 1.73 [s, 27H,
(w), 823 (w), 720 (m), 682 (w). Anal. Calc. for C21
H
34AuBN
6
S :
3
C(CH ], 6.60 [br s, 3H, imidazole H], 6.75 [br s, 3H, imidazole
3 3
)
C, 37.4; H, 5.1; N, 12.5. Found: C, 36.7; H, 5.1; N, 11.9%.
1
3
1
H], BH not observed; C d 28.8 [q, JC–H = 127, 9C, C(CH
3
)
3
],
], 114.7 [d, JC–H = 201, 3C, imidazole C],
19.9 [d, JC–H = 193, 3C, imidazole C], 159.6 [s, 3C, C=S]. IR
1
5
8.5 [s, 3C, C(CH
3 3
)
8
.
X-Ray structure determinations
1
1
data: 2975 (m), 2922 (w), 1638 (w), 1411 (m), 1361 (s), 1263 (w),
198 (m), 1164 (m), 1103 (m), 821 (w), 715 (m), 681 (w). Anal.
A summary of crystal data collection and refinement pa-
tBu
tBu
1
rameters for (Tm )Cu(PPh ) (1), (Tm )Ag(PPh )·H O (2),
tBu tBu
2 2 2 3 6 5
3
3
2
Calc. for C21
H
34BCuN
6
S
3
: C, 46.1; H, 6.3; N, 15.5. Found: C,
[Ag(Tm )] ·2CH Cl (3), (Tm )Au(PPh )·0.25C H Me (4),
tBu
2 6 6
4
5.9; H, 6.3; N, 15.1%.
and [Au(Tm )] ·3.5C H (5) is presented in Table 5. Suitable
crystals were selected, mounted with viscous oil and cooled to
the data collection temperatures. Data were collected either on
Bruker AXS SMART or APEX CCD diffractometers using
tBu
6
.
Synthesis of Ag(Tm
)
Methanol (25 mL) was added to a mixture of AgNO
3
(0.193 g,
˚
graphite monochromated Mo-Ka radiation (k = 0.71073 A).
tBu
0
.991 mmol) and Na(Tm ) (0.497 g, 0.993 mmol), resulting
Unit cell parameters were obtained from three sets of 20 frames
in the formation, within 5 min, of a white suspension. After
stirring the suspension for an additional 1 h and adding a small
amount of water (ca. 5 mL), the white product was isolated by
◦
using 0.3 scans from different sections of the Ewald sphere.
Data sets were corrected for absorption using different versions
22
of SADABS multiscan methods. No symmetry higher than
filtration, washed with water (10 mL) and dried in vacuo for 18 h
tBu
tBu
◦
triclinic was observed for Ag(Tm ) nor (Tm )Au(PPh
3
). Sys-
(
0.468 g, 81%). Mp 245 C (decomp.). NMR data (in CDCl
3
):
tematic absences in the diffraction data and unit cell parameters
1
H d 1.75 [s, 27H, C(CH
3
)
3
], 6.46 (br s, 3H, imidazole H), 6.81
tBu
¯
are consistent for Cc and C2/c for Au(Tm ), R3, R3, R32, R3m,
1
3
1
(
1
3
(
1
1
br s, 3H, imidazole H), BH not observed; C d 28.7 [q, JC–H
=
¯
tBu
¯
¯
and R3m for (Tm )Cu(PPh
3
), and P3, P3, P321, P3m1, P3m1,
1
27, 9C, C(CH
3
)
3
], 58.5 [s, 3C, C(CH
3
)
3
], 115.1 (d, JC–H = 198,
¯
tBu
P312, P31m, and P31m for (Tm )Ag(PPh
symmetry and occupancy observed for (Tm )Cu(PPh
consistent only for R3. In a similar fashion, only P3 and P321
3
). The molecular
1
C, imidazole C), 119.4 (d, JC–H = 188, 3C, imidazole C), 160.3
tBu
3
) is
s, 3C, C=S). IR data: 2976 (m), 2924 (w), 1638 (w), 1561 (w),
¯
481 (w), 1411 (m), 1397 (m), 1384 (m), 1359 (vs), 1277 (m),
198 (m), 1163 (m), 1104 (m), 1060 (w), 820 (w), 722 (w), 683
tBu
afford the proper symmetry and occupancy for (Tm )Ag(PPh
3
).
tBu
In all the structures, except that of (Tm )Cu(PPh
3
), the cen-
(
w), 559 (w), 478 (w). Anal. Calc. for C21
H
34AgBN
6
3
S : C, 43.1;
trosymmetric space group option yielded chemically reasonable
and computationally stable results of refinement. Structures
were solved using direct methods and refined with full-matrix
H, 5.9; N, 14.4. Found: C, 42.9; H, 6.0; N, 13.7%.
tBu
7
. Synthesis of Au(Tm )
2
least-squares methods based on F . The Flack parameter for
tBu
tBu
Methanol (10 mL) was added to a mixture of Na(Tm ) (0.300 g,
.599 mmol) and (tht)AuCl (0.192 g, 0.599 mmol), resulting in
(Tm )Cu(PPh ) refined to 0.46(1) suggesting a racemically
3
0
twinned data crystal and the true hand of the data-set could not
tBu
the formation of a brown solution. After stirring for 1 h, the
solution was filtered and the filtrate was concentrated under
reduced pressure to ca. 5 mL. Addition of water (5 mL) resulted
be determined. The dimeric molecule in Ag(Tm ) is located
tBu
on an inversion center. The structures of (Tm )Cu(PPh )
3
tBu
and (Tm )Ag(PPh
3
) are located on three-fold rotation axes.
in the separation of a beige solid, which was isolated by filtration
Four symmetry unique but chemically similar molecules of
◦
tBu
and dried in vacuo for 18 h (0.355, 88%). Mp 227–229
C
(Tm )Au(PPh
structures display co-crystallized solvent molecules: Ag(Tm
3
) are located in the asymmetric unit. Several
1
tBu
(
decomp.). NMR data (in CDCl
3
): H d 1.80 [s, 27H, C(CH
3
)
3
],
)
)
1
3
tBu
6
.84 [br s, 6H, imidazole H], BH not observed; C d 29.0 [q,
has one CH
2
Cl
2
disordered in two positions, (Tm )Ag(PPh
3
Table 5 Crystal, intensity collection, and refinement data
(
(
TmtBu)Cu(PPh3)
1)
(TmtBu)Ag(PPh3)·H2O Ag(TmtBu)]2·2CH2Cl2
(TmtBu)Au(PPh3)·0.25C6H5Me [Au(TmtBu)]2·3.5C6H6
(2)
(3)
(4)
(5)
Formula
Formula weight
Crystal system
Space group
a/A˚
C39H49BCuN6PS3
803.34
C39H51AgBN6OPS3
865.69
C44H72Ag2B2Cl4N12S6
1340.66
C40.75H51AuBN6PS3
959.80
C63H89Au2B2N12S6
1622.38
Trigonal
R3 (no. 146)
16.2864(7)
16.2864(7)
12.9249(11)
90
90
120
2969.0(3)
3
Trigonal
Triclinic
Triclinic
Monoclinic
C2/c (no. 15)
32.118(9)
18.662(5)
25.695(7)
90
114.016(3)
90
14068(7)
8
¯
¯
¯
P3 (no. 147)
P1 (no. 2)
P1 (no. 2)
13.7388(6)
13.7388(6)
12.8691(11)
90
90
120
11.1232(6)
11.1843(6)
13.7964(8)
95.443(1)
112.811(1)
106.636(1)
1474.14(14)
1
20.4526(17)
20.5057(18)
21.9610(19)
74.297(1)
81.811(1)
82.151(1)
3212(3)
b/A˚
c/A˚
◦
a/
b/
◦
◦
c /
V/A˚
3
2103.7(2)
2
Z
8
T/K
213(2)
0.71073
1.348
0.787
6412
213(2)
0.71073
1.367
0.704
11327
100(2)
0.71073
1.510
1.101
213(2)
0.71073
1.461
3.586
120(2)
0.71073
1.531
4.391
Radiation (k/ A˚ )
−
3
Dc/g cm
l(Mo-Ka)/mm
Reflections collected
−
1
11677
17720
28782
Independent reflections (Rint) 2725 (0.0568)
3301 (0.0287)
157
0.0489; 0.1373
0.0535; 0.1403
1.141
6235 (0.0190)
471
0.0331; 0.0785
0.0383; 0.0808
1.095
39270 (0.0289)
1900
0.0438; 0.1043
0.0668; 0.1162
1.022
10079 (0.0769)
784
0.0445; 0.0786
0.0712; 0.0891
1.013
No. of parameters
160
a
R1; wR2 [I > 2r(I)]
0.0427; 0.0992
0.0440; 0.1000
1.036
a
R1; wR2 (all data)
GOF
ꢀ[w(F
− F
) ]/
ꢀ(wF
) } ; R(F) =
ꢀD/ꢀ|F
|, D = ꢁF
| − |F
ꢁ; w = [r (F
) + (aP) + bP]−1; P = [2F 2
+
a
2
2
2
2
2
2
1/2
2
2
2
Quantity minimized = R(wF ) = {
Max(F ,0)]/3.
o
c
o
o
o
c
o
c
o
D a l t o n T r a n s . , 2 0 0 5 , 2 4 1 0 – 2 4 1 6
2 4 1 5

View Online
has one H
2
O molecule located at a three-fold rotation axis,
G. Valle and S. Calogero, Polyhedron, 1998, 17, 3201; (c) G. Gioia
tBu
(
Tm )Au(PPh ) has one toluene molecule in the asymmet-
3
Lobbia, J. V. Hanna, M. Pellei, C. Pettinari, C. Santini, B. W. Skelton
and A. H. White, Dalton Trans., 2004, 951.
tBu
ric unit, and Au(Tm ) displays four benzene molecules, one
of which is located at a two-fold rotation axis yielding an
equivalent of 3.5 benzene molecules per asymmetric unit. The
hydrogen atoms in Ag(Tm ) and the hydrogen atom attached to
boron of (Tm )Cu(PPh
difference map with occupancies and isotropic displacement
parameters based on the bonded non-hydrogen atom. All other
hydrogen atoms were treated as idealized contributions except
those on the disordered water molecule in (Tm )Ag(PPh )
which were ignored. All structure factors and anomalous
displacement parameters are included in various versions of the
1
1
3 (a) M. C. Gimeno and A. Laguna, Chem. Rev., 1997, 97, 511;
(
2
b) M. A. Carvajal, J. J. Novoa and S. Alvarez, J. Am. Chem. Soc.,
004, 126, 1465.
tBu
4 A. A. Mohamed, D. Rabinovich and J. P. Fackler, Acta Crystallogr.,
tBu
3
) were located from the electron density
Sect. E, 2002, 58, m726.
◦
15 The original trigonality index s = (b − a)/60 was introduced to
measure the deviation from the ideal square pyramidal (s = 0) and
trigonal bipyramidal (s = 1) geometries in five-coordinate complexes.
See: A. W. Addison, T. N. Rao, J. Reedijk, J. van Rijn and G. C.
Verschoor, J. Chem. Soc., Dalton Trans., 1984, 1349.
tBu
3
1
6 (a) O. E. Piro, E. E. Castellano, R. C. V. Piatti, A. E. Bolz a´ n and
A. J. Arvia, Acta Crystallogr., Sect. C, 2002, 58, m252; (b) I. Garcia
Santos, A. Hagenbach and U. Abram, Dalton Trans., 2004, 677; (c) S.
Friedrichs and P. G. Jones, Acta Crystallogr., Sect. C, 1999, 55, 1625;
22
SHELXTL program library.
CCDC reference numbers 270369–270373.
See http://dx.doi.org/10.1039/b506046j for crystallographic
data in CIF or other electronic format.
(
d) S. Friedrichs and P. G. Jones, Z. Naturforsch., Teil B, 2004, 59,
4
7
1
9; (e) S. Friedrichs and P. G. Jones, Z. Naturforsch., Teil B, 2004, 59,
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We thank the Camille and Henry Dreyfus Foundation, Inc. for
a Henry Dreyfus Teacher–Scholar Award to D. R., Research
Corporation for a Cottrell College Science Award, the donors
of the Petroleum Research Fund, administered by the American
Chemical Society, the National Science Foundation (Award
No. CHE-0316723) and The University of North Carolina at
Charlotte for support of this research. D. J. M. is also grateful
to the Thomas D. Walsh Tuition Fellowship Fund for financial
assistance.
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