3,3″-bis(saccharin-6-ylmethyl)-1,1′:3′,1″-terphenyl - Precursor of a new tetradendate bis-bridging ligand

Article abstract of DOI:10.5560/ZNB.2012-0143

The title compound (H2tpsac) was synthesized from 6-bromosaccharin and 3,3"-bis(bromomethyl)-m-terphenyl. The ability of tpsac to serve as a tetradentate bis-bridging ligand was demonstrated by the formation of the dinuclear ruthenium(I,I) complexes [Ru₂(CO)₅(μ,μ- tpsac)]₂, [Ru₂(CO)4(μ,μ-tpsac)]_n, [Ru₂(CO)₄(PPh₃)₂(μ,μ-tpsac)], and [Ru₂(CO)₅(PPh₃)(μ,μ-tpsac)]. An X-ray crystal structure analysis of [Ru₂(CO)₄(PPh ₃)₂(μ,μ-tpsac)] showed the head-to-tail (or 1,1) arrangement of the two saccharinate coordination sites.

Full text of DOI:10.5560/ZNB.2012-0143

3,300-Bis(saccharin-6-ylmethyl)-1,10:30,100-terphenyl – Precursor of A New
Tetradendate Bis-bridging Ligand
Stefan Buck and Gerhard Maas
Institut fu¨r Organische Chemie I, Universita¨t Ulm, Albert-Einstein-Allee 11, 89081 Ulm,
Germany
Reprint requests to Prof. Dr. Gerhard Maas. Fax: +49 731 5022803.
E-mail: gerhard.maas@uni-ulm.de
Z. Naturforsch. 2012, 67b, 1070 – 1080 / DOI: 10.5560/ZNB.2012-0143
Received May 22, 2012
Dedicated to Professor Heribert Offermanns on the occasion of his 75th birthday
The title compound (H2tpsac) was synthesized from 6-bromosaccharin and 3,300-bis(bromo-
methyl)-m-terphenyl. The ability of tpsac to serve as a tetradentate bis-bridging ligand was
demonstrated by the formation of the dinuclear ruthenium(I,I) complexes [Ru2(CO)5(µ,µ-tpsac)]2,
[Ru2(CO)4(µ,µ-tpsac)]n, [Ru2(CO)4(PPh3)2(µ,µ-tpsac)], and [Ru2(CO)5(PPh3)(µ,µ-tpsac)]. An
X-ray crystal structure analysis of [Ru2(CO)4(PPh3)2(µ,µ-tpsac)] showed the head-to-tail (or 1,1)
arrangement of the two saccharinate coordination sites.
Key words: Ruthenium Complexes, Saccharin, Ligands
Introduction
carbenoid reactions, and recent computational work
seems to support this assumption (see, for example,
Dinuclear rhodium(II,II) carboxylates and amidates refs. [4 – 6]). On the other hand, in order to explain
of the type Rh2(µ-L)4 (L = bidentate ligand) are ef- the enantioselectivity observed for alkyne cycloprope-
ficient catalysts for intramolecular and intermolecular nation with ethyl diazoacetate, Corey and co-workers
carbenoid reactions of diazo compounds [1]. While ex- have proposed a mechanism that involves the com-
perimental evidence and computational results nowa- plete dissociation of one carboxylate ligand followed
days corroborate the mechanistic hypotheses of short- by [2+2] cycloaddition of the alkyne to the resulting
lived rhodium-carbene intermediates and their chem- tribridged rhodium-carbene complex [7, 8].
ical and stereochemical mode of interaction with sub-
We have recently synthesized a variety of dinuclear
strate molecules, it is still not clear which role is played tetracarbonyldiruthenium(I,I) carboxylate and amidate
by ligand dynamics in the catalytic process and to complexes, Ru2(CO)4(µ-L)2, and have studied them as
which extent it affects the catalyst’s lifetime under the alternative catalysts for carbene transfer reactions with
reaction conditions. The mentioned complexes Rh2(µ- diazo compounds [9 – 13]. These diruthenium com-
L)4 have a paddlewheel structure with the chelating plexes have the typical sawhorse structure [14] with
ligands in equatorial positions; in a rhodium-carbene the two bidentate ligands in cis-configuration. Exam-
complex, the carbene ligand occupies the available ax- ples are shown in Fig. 1. With the unsymmetrical ami-
ial coordination site at one rhodium center, similar to date ligands, which coordinate by an N−C=O moi-
the coordination of neutral Lewis base ligands such ety, head-to-tail (or 1,1, e. g. 1 and 3) and head-to-
as water, amines and nitriles (for the first X-ray crys- head (or 0,2, e. g. 2 and 4) complexation is possible.
tal structure determination of a Rh2(tBuCOO)4 com- Our investigations on saccharinato- (1 and 2 [12]) and
plex bearing an axial NHC ligand, see ref. [2]; for 2-pyridinolato- (3 and 4 [3, 10]) tetracarbonyldiruthe-
a related Ru(I,I)-NHC complex, see ref. [3]). It has nium(I,I) complexes have shown that the mutual con-
generally been assumed that the tetrabridged dinuclear version of the (1,1) and (0,2) arrangements of the equa-
framework of a rhodium-carbene remains intact during torial bidentate ligands can occur smoothly at room
c
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S. Buck – G. Maas · 3,300-Bis(saccharin-6-ylmethyl)-1,10:30,100-terphenyl
1071
catalyst. Intramolecular bridging of two carboxylato
or amidato moieties has been envisaged to alleviate
this problem; this would prevent a dissociating lig-
and to leave the complex completely, and it could
enhance the structural stability of the complex with
respect to (1,1)/(0,2) isomerization in the case of
the unsymmetrical amidato ligands. In fact, a number
of dirhodium complexes with tethered dicarboxylato
ligands have become known recently [15 – 23]. We
have prepared bis(calixarenedicarboxylato)dirhodium
complexes and analogous (calixarenedicarboxy-
lato)tetracarbonyldiruthenium complexes such as 5
(Fig. 1) [17]. Both types of complexes were active
catalysts for carbenoid reactions of diazo com-
pounds (cyclopropanation, intramolecular C–H inser-
tion) [11, 13, 17], although a significant advantage
over simple dirhodium tetracarboxylates could not be
seen. Taber’s first dirhodium complex with a tethered
dicarboxylate ligand was highly efficient and effective
in an intramolecular carbenoid C–H insertion [15].
Complex Rh2(esp)2 (6) performed exceptionally ef-
fective and versatile in catalytic C–H bond amination
reactions under oxidative conditions [21, see also
23], and it was better suited than simple dirhodium
tetracarboxylates for the cyclopropanation of mono-
and cis-disubstituted olefins [24].
O2S
L1
O2S
O
N
N
O
SO2
CO
CO
L2
Ru
O
N
L1
N
Ru L2
CO
Ru
Ru
O
OC OC
O2S
CO
CO
CO
1
2
L1 = L2 = CO
L1 = CO, L2 = PPh3
L1 = L2 = CH3CN
1 = L2 = PPh3
L
Hal
N
O
Hal
N
O
O
N
CO
CO
O
Hal
L1 Ru
OC CO
CO
Ru L2
Ru
Ru
L
Hal
N
CO
CO
CO
3
4
L1 = L2 = CO
L = PPh3, CH3OH
L1 = L2 = CH3CN
L
1 = L2 = PPh3
CO
CO
OC
OC
Ru
Ru
O
O
O
O
O
O
Br
O
Br
O
Rh Rh
O
As far as we know, dinuclear complexes containing
two tethered saccharin moieties as briding ligands have
not been reported. For the design of a suitable ligand,
we considered the solid-state structure of the diruthe-
nium complex 1 (L1 = L2 = CH3CN) [12], where
the distance between the C-6 ring positions of the two
O
O
O
O
O
O
O
Pr
Pr
Pr
Pr
5
6
Fig. 1. Dinuclear Ru(I,I) and Rh(II,II) complexes relevant to
this study.
˚
cis-oriented saccharin ligands is 8.16 A. We speculated
that this distance could be bridged with a 1,10:30,100-
terphenyl-3,300-dimethyl structural moiety, more rigid
temperature during exchange of the axial ligands. For
6-halogenopyridin-2-olato complexes [Ru2(CO)4(µ-
HalpyO)2(L1/2)], solvent- and temperature-dependent
equilibria between (1,1) and (0,2) species could be
observed in solution by NMR spectroscopy [3] in
the temperature range where carbenoid reactions with
these complexes as catalysts are usually performed.
It is obvious that the presence of constitutional
equilibria in the catalytically active complexes can
be an obstacle to the design of catalysts, particularly
with respect to the diastereo- and enantioselectivity
of the envisaged catalyzed reactions. Additionally,
complete dissociation of a chelating ligand from
O
O
S
S
NH
NH
O
O
O
O
7
the dinuclear core may facilitate degradation of the Fig. 2. The title compound 7.
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S. Buck – G. Maas · 3,300-Bis(saccharin-6-ylmethyl)-1,10:30,100-terphenyl
O
O
than a linear alkyl chain but still flexible enough to ac-
commodate the new bis-saccharinate ligand in a rather
unstrained complex geometry. We report here on the
synthesis of the ligand precursor 7 (Fig. 2) and tetracar-
bonyldiruthenium(I,I) complexes derived from it.
(i)
(ii)
NH
N
Bn
S
S
Br
Br
O
O
O
O
Br
11
12
O
O
(iv)
(iii)
N
Bn
N
O
Bn
Results and Discussion
O
HO
S
S
B
B
O
O
O
O
HO
Synthesis of bis-saccharin 7 (H2tpsac)
13
14
Scheme 2. (i) ref. [26], 3 steps, overall yield 22%; (ii) 1.
NaH, DMF; 2. BnBr, r. t., 2 d, then 80 ◦C, 3 h, 84% yield; (iii)
bis(pinacolato)diboron (1.32 equiv.), KOAc (3.92 equiv.),
PdCl2(dppf)·CH2Cl2 (3 mol-%), 1,4-dioxane, 90 ◦C, 12 h,
73% yield; (iv) NaIO4, 2 M HCl, acetone/H2O, r. t., 12 h,
96% yield; Bn = benzyl.
Bis-saccharin 7 was assembled in a convergent man-
ner from 3,300-bis(bromomethyl)-m-terphenyl (9) and
saccharin building blocks 13 or 14. At first, terphenyl
8 [25] was prepared from 1,3-diiodobenzene and 3-
methylphenylboronic acid by a Suzuki-Miyaura reac-
tion (Scheme 1). The conversion of 8 into the dibro-
mide 9 was achieved by photochemical bromination
with NBS in dichloromethane. Tetrabromide 10 was
formed as a minor by-product (9:10 ≈ 11) which could
not be removed easily by crystallization or chromatog-
raphy. However, it was possible to use this mixture
for the subsequent coupling reaction. The usual ther-
mally activated Wohl-Ziegler bromination (NBS and
dibenzoyl peroxide in CCl4 [20]) gave a significantly
higher amount of the tetrabromide 10 (> 20% yield)
even when NBS was added in small portions.
(iii)
(i) or (ii)
7
Br
Br
O
O
9
S
S
N
N
O
O
O
Bn
O
Bn
15
Scheme 3. (i) 13 (2.2 equiv.), PdCl2(dppf)·CHCl3 (cat.),
Cs2CO3 (2 equiv.), THF/H2O, 80 ◦C, 12 h, 48% yield;
(ii) 14 (2.6 equiv.), Pd(PPh3)4 (cat.), Na2CO3 (7 equiv.),
toluene/EtOH/H2O, 90 ◦C, 12 h, 76% yield; (iii) 1.
HCOONH4, Pd/C, EtOH, reflux, 12 h; 2. 1 M HClaq; 84%
yield.
The saccharin building blocks 13 and 14 were ob-
tained from 6-bromosaccharin (11) [26] as shown in
Scheme 2. N-Protection with NaH/benzyl bromide in
DMF [27] gave 12, which was converted into (N-
benzylsaccharin-6-yl)boronic acid pinacol ester (13) obtained with insufficient purity. Boronic acid ester 13
by Pd-catalyzed boration. The boration of unprotected could be cleaved with sodium periodate/HCl [29] to
6-bromosaccharin (11) under the same conditions has give the (N-benzylsaccharin-6-yl)boronic acid 14 al-
been described in a patent [28], but the product was most quantitatively.
The terphenyl/saccharin conjugate 15 was obtained
by Suzuki-Miyaura coupling of dibromide 9 and ei-
ther dioxaborolane 13 or boronic acid 14 (Scheme 3).
With the boronic acid and standard reaction condi-
B(OH)2
(i)
+
I
I
tions (Pd(PPh3)4, Na2CO3, toluene/EtOH/H2O) a sig-
nificantly better yield of 15 (76%) was obtained.
N-Deprotection of 15 was achieved by transfer hy-
drogenation [30] and furnished the ligand precursor
H2tpsac (7).
8
(ii)
+
Tetracarbonyldiruthenium(I,I) complexes with the
tpsac ligand
Br
Br
Br
Br
Br
Br
9
10
Scheme 1. (i) Pd(PPh3)4 (cat.), Na2CO3, 1,4-dioxane/H2O,
90 ◦C, 12 h, 88% yield; (ii) N-bromosuccinimide, CH2Cl2,
hν, mixture of 9 (46%) and 10 (4%).
Based on our previous experience with the synthesis
and structures of diruthenium(I,I) saccharinate com-
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S. Buck – G. Maas · 3,300-Bis(saccharin-6-ylmethyl)-1,10:30,100-terphenyl
1073
plexes such as 1 and 2 [12], we wondered whether
Heating of complex 17 in refluxing toluene for four
similar complexes could be obtained with the bis- days yielded a greenish-gray solid which was identi-
saccharin H2tpsac (7). Two coordination patterns could fied as the dinuclear complex [Ru2(CO)4(µ,µ-tpsac)]n
be expected – the tetradentate ligand tpsac could either (18). The polymeric structure is maintained by head-
coordinate intramolecularly with both N−C=O moi- to-tail dimerization across the Ru–O bonds and re-
eties at the same diruthenium core to form a discrete 1 : quires the dinuclear repeating unit to exist in the head-
1 complex, or it could coordinate with each N−C=O to-tail (1,1) arrangement of the bis-saccharinato ligand.
moiety at a different Ru2 core giving rise to oligo- or Because of its polymeric nature, 18 is only soluble in
polymeric chains or supramolecular macrocyclic struc- certain donor solvents, such as in hot DMSO. In addi-
tures. We were pleased to find that the intramolecular tion to an elemental analysis, the structural assignment
coordination motif was realized. This is remarkable, is supported by the absence of an IR absorption for ax-
because the tpsac ligand is a conformationally flexi- ial CO ligands and by the typical absorption pattern
ble ligand for which the two amidate coordination sites of an M2(CO)4 unit [14, 32, 33] (ν = 2046 vs, 1995 s,
do not appear to be as much pre-organized as, e. g., 1962 vs cm−1).
in calix[4]arenedicarboxylates (compare structure 5,
Fig. 1).
As expected, the axial Ru···O coordination in the
dimeric complex 17 and in the polymeric complex 18
When H2tpsac was heated with Ru3(CO)12 in could be cleaved by the action of better donor lig-
toluene under reflux conditions, a brown solid of un- ands. Thus, complex 17 reacted with two equivalents
known constitution was obtained which was insoluble of triphenylphosphane (relative to a monomeric Ru22+
in common organic solvents including DMSO and ace- complex unit) in dichloromethane to give a yellow
tonitrile. However, when the reaction was performed solid, the 31P NMR spectrum of which displayed sig-
at 130 ◦C in a closed pressure Schlenk tube (so that nals at δP (CDCl3) = 14.4 and 23.6 ppm in a 10:1 ra-
evolved carbon monoxide could not escape), a yel- tio. While the major signal is attributed to the bis-PPh3
low solution was formed; after completion of the re- complex [Ru2(CO)4(PPh3)2(µ,µ-tpsac)] (19), the mi-
action and work-up, a yellow solid was isolated which nor signal is likely to belong to the mono-PPh3 com-
after removal of most of the solvent in vacuo turned plex [Ru2(CO)5(PPh3)(µ,µ-tpsac)] (20). The presence
light-brown. The structure of the dimeric complex of an axial CO ligand in 20 was indicated by a rather
[Ru2(CO)5(µ,µ-tpsac)]2 (17) is tentatively assigned to weak absorption at 2085 cm−1 in the IR spectrum of
this solid, based on the presence of an IR absorp- the mixture of 19 and 20. These observations and in-
tion indicating an axial CO ligand (ν = 2096 cm−1
)
terpretations are in agreement with those for the analo-
in addition to the absorptions caused by equatorial gous diruthenium complexes containing two sacchari-
CO ligands (ν = 2040, 2013, 1946 cm−1), the solubil- nate ligands, which in contrast to 19/20 could be sepa-
ity in hot chloroform, and the subsequent transforma- rated [12]. While the tpsac ligand in complex 19 adopts
tions. Unfortunately, a correct elemental analysis could the head-to-tail arrangement (vide infra), the mono-
not be obtained, because the solid strongly retained PPh3 complex 20 is likely to have the head-to-head
some toluene even when kept at 150 ◦C/0.001 mbar constitution, with the PPh3 ligand occupying the ster-
for one hour. An analogous structure has been pos- ically less congested axial position, in agreement with
tulated for the saccharinato complex [Ru2(CO)5(µ,µ- the known molecular structure of the analogous com-
sac)2]2 [12], and the structure of the related com- plex [Ru2(CO)5(PPh3)(µ-sac)2] [12].
plex [Ru2(CO)5(µ,µ-6-fluoropyridin-2-olate)2]2 was
Treatment of the coordination polymer 18 with
proven by XRD analysis [31]. Notably, the antic- two equivalents of triphenylphosphane in CDCl3
ipated precursor to 17, the hexacarbonyl complex gave the monomeric complex [Ru2(CO)4(PPh3)2(µ,µ-
[Ru2(CO)6(µ,µ-tpsac)] (16), could neither be isolated tpsac)] (19) almost quantitatively. The 31P NMR
nor observed directly, in contrast to the analogous sac- spectrum showed, besides the signal of 19 (δP =
charinato complex [Ru2(CO)6(µ,µ-sac)2] [12]. It ap- 14.4 ppm), the presence of a very minor second species
pears that 16 loses one or even both axial CO ligands (δP = 22.3 ppm), which could be the mono-PPh3
very easily, and that a clean reaction yielding complex complex [Ru2(CO)4(PPh3)(µ,µ-tpsac)] (20) (however,
17 is only possible in the presence of a carbon monox- note the small difference in δP values compared
ide atmosphere.
with 20 obtained from 17) or the analogous complex
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S. Buck – G. Maas · 3,300-Bis(saccharin-6-ylmethyl)-1,10:30,100-terphenyl
7
toluene
toluene
(3 equiv)
+
130 °C, 12 h, p
109 °C, 4 d
[Ru2(CO)6(µ-tpsac)]
− CO
Ru3(CO)12 (2 equiv)
16
O2S
O
O2S
O2S
N
O
N
N
O
SO2
O
N
OC Ru Ru
Ru Ru
OC OC
n
CO
CO
OC
2
CO
CO
CO
18
17
2 PPh3
CH2Cl2, r.t.
17 18
or
+
O2S
O
O2S
O2S
N
O
N
N
SO2
O
O
N
Ph3P
Ru Ru PPh3
OC Ru Ru PPh3
CO
OC
OC
CO
OC
CO
CO
CO
19
20
Scheme 4. Formation of dinuclear Ru(I,I) complexes 16–20.
[Ru2(CO)4(PPh3)(µ,µ-tpsac)] with no axial CO ligand
(Scheme 4).
1
It should be noted that the H and 13C NMR spec-
tra of the tpsac complexes reported here in all cases
show more signals than expected from their compo-
sition. This is likely due to the presence of the m-
terphenyl-3,300-dimethyl bridge, which can exist in dif-
ferent diasteroisomeric conformations that are stable
on the NMR time scale. Due to signal overlap and par-
tial line broadening, a detailed interpretation was not
undertaken.
Single crystals of [Ru2(CO)4(PPh3)2(µ,µ-tpsac)]
(19, prepared from 18) were obtained, which were
suited for an X-ray crystal structure determination.
Fig. 3 shows the molecular structure of 19. The two
amidate coordination sites of the tpsac ligand are
in cis-position and assume a head-to-tail constitu-
tion; furthermore the complex has a crystallographic
C2 symmetry in the solid state. Characteristic bond
geometry data are provided in Table 1. While the
bond lengths agree well with the data reported for
[Ru2(CO)4(PPh3)2(µ-sac)2] (1, Fig. 1) featuring two
non-tethered saccharinato ligands [12], bond angles
and torsion angles in part assume different values to ac-
Fig. 3 (color online). Solid-state structure of the C2-
symmetrical complex 19. Displacement ellipsoids are shown
at the 20% probability level.
commodate the steric requirements imposed by the ter- the terphenyl bridge, the outer phenyl rings are tilted
phenyl bridge. Thus, the N–Ru–O bond angle is 85.3◦ against the central ring by about 40◦.
in 19 and 88.5◦ in 1 (L1 = L2 = PPh3, Fig. 1), and the
The catalytic activity of the new complexes 17
0
˚
C6–C6 distance is 7.58 A in the bridged complex 19 and 18 was tested on the cyclopropanation of
˚
compared to 8.16 A in the unbridged complex 1. In styrene with methyl diazoacetate to give methyl 2-
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S. Buck – G. Maas · 3,300-Bis(saccharin-6-ylmethyl)-1,10:30,100-terphenyl
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Table 1. Selected bond lengths
(A), angles (deg), and torsion
angles (deg) for 19 with esti-
mated standard deviations in
parentheses.
Distances
Ru–Ru0
Ru–P
Ru–C1
Ru–C2
Ru–O5
Ru–N
Angles
Torsion angles
˚
2.7504(13) C1–Ru–Ru0
94.0(2)
88.6(2)
N–Ru–Ru0–O50
–24.1(4)
–117.3(4)
–30.2(4)
–5.5(8)
2.462(2)
1.814(7)
1.860(7)
2.117(4)
2.170(4)
1.334(7)
1.259(6)
C2–Ru–Ru0
P–Ru–Ru0
C1–Ru–C2
C1–Ru–O5
C1–Ru–N
C2–Ru–O5
O5–Ru–N
C1–Ru–Ru0–C10
172.08(5) C1–Ru–Ru0–C20
87.2(3)
175.6(2)
90.9(2)
96.1(2)
85.3(2)
Ru–N–C3–O50
C3–N
C3–O50
N2=CHCO2Me
catalyst (1 mol-%)
CH2Cl2. r. t.
Experimental Section
Ph
H
H
+
General information
Ph
−N2
Ph
CO2Me
CO2Me
(Z)-21
Ru3(CO)12 (ABCR) and PdCl2(dppf)·CH2Cl2 (ChemPur)
were purchased and used as supplied; PdCl2(dppf)·CHCl3
was prepared as described [34]. Solvents were dried by
known procedures and stored under argon, most reactions
were carried out using a standard Schlenk technique. Col-
umn chromatography was performed using silica gel 60
(Macherey-Nagel, 0.063 – 0.2 mm). Petroleum ether with
a b. p. range of 40 – 60 ◦C was used.
NMR spectra were recorded using a Bruker DRX 400
spectrometer (1H: 400.13 MHz, 13C: 100.61 MHz; 31P:
161.98 MHz). The 1H and 13C spectra were referenced to
the residual proton signal of the solvent; 1H: δ(CHCl3) =
7.26, δ((CH3)2SO) = 2.50, δ(CH2Cl2) = 5.31 ppm; 13C:
δ(CDCl3) = 77.0, δ((CD3)2SO) = 39.5, δ(CD2Cl2) =
53.7 ppm. The 31P NMR spectra were referenced to 85%
H3PO4 as an external standard (δP = 0 ppm). IR spectra were
recorded on KBr pellets with a Bruker Vector 22 FTIR instru-
ment. Mass spectra: ESI(+): Waters Micromass ZMD instru-
ment; CI(+): Finnigan-MAT SSQ-7000, 100 eV, methane as
reagent gas. Elemental analyses were obtained with an ele-
mentar Hanau vario MICRO cube analyzer. Melting points
were determined with a Bu¨chi B-540 instrument at a heat-
ing rate of 2 ◦C min−1 (if not stated otherwise). Differential
scanning calorimetry (DSC): Perkin Elmer DSC 7 calorime-
ter.
(E)-21
17
cat.
cat. 18
51 %; Z:E = 59:41
26 %; Z:E = 52:48
cat. [Ru2(CO)5(µ-sac)2]2 76 %; Z:E = 64:36
cat. [Ru2(CO)4(µ-sac)2]n 54 %; Z:E = 52:48
Scheme 5. Comparison of catalysts for carbenoid cyclo-
propanation of styrene. Reaction conditions: the catalyst was
suspended in styrene/CH2Cl2, and the diazoacetate dissolved
in CH2Cl2 was gradually added; styrene : diazoester = 10 : 1.
phenylcyclopropane-1-carboxylates (Z)- and (E)-21
(Scheme 5). It is known that the diazo compound is
able to cleave the Ru···O bonds maintaining the coor-
dination dimer and polymer. The comparison with the
results obtained by us for closely related untethered
bis(saccharinato) catalysts [12] shows that the yields
with 17 and 18 as catalysts are lower, and the diastere-
omeric ratio is more or less the same. Thus, the teth-
ered bis-sacharinato ligand of 17 and 18 offers no ad-
vantage in this case.
Conclusion
3,300-Dimethyl-1,10:30,100-terphenyl (8)
The ability of the new tetradentate bis-saccharinato
ligand tpsac to bridge a tetracarbonyldiruthenium core
by µ,µ-coordination of the two amidate units has
been demonstrated. Several complexes of the type
[Ru2(CO)4(µ,µ-tpsac)L1L2] were synthesized. All of
them have the two bridging amidate groups in cis-
position, but depending on the axial ligands L1 and L2,
they exist either in the head-to-tail or the head-to-head
constitution. Although equilibria between the two con-
stitutions were not observed directly, it is obvious that
in spite of the terphenyl bridge, constitutional changes
can occur smoothly during the synthesis of the differ-
ent complexes.
A solution of 1,3-diiodobenzene (4.02 g, 12.2 mmol) and
3-methylphenylboronic acid (3.62 g, 26.6 mmol) in 1,4-
dioxane (20 mL) was prepared in a thick-walled Schlenk
tube, and an aqueous solution of Na2CO3 (2 M, 30 mL) and
Pd(PPh3)4 (0.43 g, 0.36 mmol) were added. The mixture was
stirred at 90 ◦C overnight. After cooling, the solvent was
evaporated and the residue was extracted with 2 × 30 mL
of diethyl ether. The combined ether phases were extracted
with hydrochloric acid (2 M, 10 mL) and water (20 mL).
After drying (Na2SO4) and evaporation of the solvent, the
residue was worked up by column chromatography over sil-
ica gel (140 g, petroleum ether) to give 8 as a clear viscous
Unauthenticated
Download Date | 1/10/17 7:57 AM

1076
S. Buck – G. Maas · 3,300-Bis(saccharin-6-ylmethyl)-1,10:30,100-terphenyl
oil (2.80 g, 88%) (lit. [25]: m. p. 54 ◦C). – C20H18 (258.4): stirred until gas evolution had ceased. After addition of ben-
calcd. C 92.98, H 7.02; found C 93.17, H 7.02. 1H and 13
NMR data fully agreed with the reported ones [25].
C
zyl bromide (0.22 mL, 1.9 mmol), the reaction mixture was
stirred at r. t. for two days, then at 80 ◦C for 3 h. Wa-
ter (5 mL) was added, and the mixture was extracted with
ethyl acetate (3 × 15 mL). The organic phase was washed
with aq. HCl (1 M, 5 mL), saturated aqueous NaHCO3 so-
lution (5 mL) and brine (5 mL), then dried with Na2SO4.
After filtration the solvent was evaporated, and the residue
was stirred in petroleum ether (10 mL), yielding product 12
as a colorless solid (0.47 g, 84%), m. p. 160–162 ◦C. – IR
(KBr): ν = 3091 w, 3073 w, 1746 vs (C=O), 1587 m, 1454
m, 1392 m, 1334 vs, 1319 s, 1278 s, 1241 s, 1169 vs, 1076
m, 1043 m, 947 m, 846 m, 747 m, 698 m, 669 m, 592
m, 522 m cm−1. – 1H NMR (CDCl3): δ = 4.89 (s, 2 H,
NCH2), 7.30–7.38 (m, 3 H, Hphenyl), 7.49 (d, J = 7.1 Hz,
2 H, Hphenyl), 7.88 (d, J = 8.1 Hz, 1 H, Haryl), 7.93 (dd,
3J = 8.1 Hz, 4J = 1.5 Hz, 1 H, Haryl), 8.05 (d, 4J = 1.5 Hz, 1
H, CHaryl) ppm. – 13C NMR (CDCl3): δ = 42.9 (NCH2),
124.2, 126.0, 126.4, 128.3, 128.68, 128.71, 129.8, 134.1,
137.6, 139.1, 158.1 (C=O) ppm. – MS (CI+): m/z (%) = 354
(100)/352 (90) [M + H]+, 81/79Br; 289 (18)/287 (18) [M –
SO2]+. – C14H10BrNO3S (352.2): calcd. C 47.74, H 2.86, N
3.98; found C 47.72, H 2.87, N 3.93.
3,300-Bis(bromomethyl)-1,10:30,100-terphenyl (9)
A solution of terphenyl 8 (1.96 g, 7.6 mmol) and N-
bromosuccinimide (3.00 g, 16.9 mmol) in dichloromethane
(50 mL) was placed in a round-bottom glass flask and ir-
radiated for 4 d with an electrical light bulb (Osram, Kryp-
ton 60 W). After extraction with saturated aqueous NaHCO3
solution (10 mL) and water (2 × 10 mL), the reaction solu-
tion was dried (Na2SO4), the solvent was evaporated, and
the remaining oil was stirred in diethyl ether (2 mL) and
petroleum ether (10 mL) until crystallization took place. The
colorless solid obtained after drying (22 ◦C/0.001 mbar) con-
sisted of dibromide 9 (1.56 g, 46% yield) and tetrabromide
10 (0.16 g, 4% yield). This mixture was used without sepa-
ration for the subsequent transformation. The NMR data of 9
were in agreement with lit. [25]. 3,300-Bis(dibromomethyl)-
1,10:30,100-terphenyl (10) was identified by the following
NMR data: 1H NMR (CDCl3): δ = 6.74 (s, 2 H, CHBr2),
7.47–7.50 (m, 2 H, Haryl), 7.60–7.64 (m, 7 H, Haryl), 7.78 (s,
1 H, Haryl), 7.82 (s, 2 H, Haryl) ppm. – 13C NMR (CDCl3):
δ = 40.8, 125.3, 125.6, 126.1, 126.7, 128.7, 129.2, 129.5,
140.9, 141.5, 142.5 ppm.
2-Benzyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-
2-yl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (13)
6-Bromobenzo[d]isothiazol-3(2H)-one 1,1-dioxide
(6-bromosaccharin) (11)
In a thick-walled Schlenk tube, a solution of N-
benzyl-6-bromosaccharin (12, 0.99 g, 2.8 mmol) and
bis(pinacolato)diboron (0.94 g, 3.7 mmol) in dry 1,3-
dioxane (30 mL) was prepared, and potassium acetate
(1.08 g, 11.0 mmol) was added. After degassing and satu-
ration with argon PdCl2(dppf)·CH2Cl2 (70 mg, 86 µmol)
was added, and the mixture was kept with stirring at 90 ◦C
overnight. After cooling the solvent was replaced by ethyl
acetate, the solution was passed over a plug of silica gel to
remove a polar impurity, and the solid obtained after evapo-
ration of the solvent was treated with boiling petroleum ether
for 10 min to remove last traces of ethyl acetate. The solid
was filtered off and dried at r. t./0.001 mbar for 1 h to leave
a light-beige powder (0.81 g, 73%), m. p. 169.9–170.3 ◦C.
– IR (KBr): ν = 2978 w, 1732 vs (C=O), 1400 m, 1364
s, 1339 vs, 1276 m, 1239 m, 1189 s, 1146 m, 1134 m,
This compound was prepared from 4-bromotoluene
via 2-chlorosulfonyl-4-bromotoluene and 2-aminosulfonyl-
4-bromotoluene as described in ref. [26], but without com-
plete purification of the intermediate products, in 22% over-
all yield. Crystallization from ethanol-water gave colorless
long needles, m. p. 227–228 ◦C (lit. [26]: 216–217 ◦C). –
IR (KBr): ν = 3407 br m, 3096 br m, 2659 w, 1737 vs
(C=O), 1705 vs (C=O), 1587 s, 1344 vs, 1331 vs, 1268 m,
1248 m, 1177 vs, 1143 m, 1123 m, 1076 m, 886 m, 854 m
cm−1. – 1H NMR (CDCl3/[D6]DMSO = 9/1): δ = 7.73 (d,
3J = 8.1 Hz, 1 H, Haryl), 7.87 (dd, 3J = 8.1 Hz, 4J = 1.5 Hz,
1 H, Haryl), 7.96 (d, 4J = 1.5 Hz, 1 H, Haryl), 8.50 (br s,
1 H, NH) ppm. – 13C NMR (CDCl3/[D6]DMSO = 9/1):
δ = 123.5, 125.9, 126.5, 129.1, 136.9, 140.7, 159.5 (NC=O)
ppm. – MS (CI+): m/z (%) = 264 (100)/262 (94, [M + H]+,
81/79Br). – C7H4BrNO3S (262.1): calcd. C 32.08, H 1.54, N
5.34; found C 32.19, H 1.55, N 5.32.
1
1091 m, 845 m, 703 m, 691 m, 593 m, 525 m cm−1. – H
NMR (CDCl3): δ = 1.37 (s, 12 H, 4 CH3), 4.90 (s, 2 H,
CH2), 7.30–7.38 (m, 3 H, Hphenyl), 7.51 (dd, 3J = 6.6 Hz,
2 H, Hphenyl), 8.01 (d, J = 7.6 Hz, 1 H, Haryl), 8.21 (d,
J = 7.1 Hz, 1 H, Haryl), 8.34 (s, 1 H, Haryl) ppm. – 13C
NMR (CDCl3): δ = 24.9 (CH3), 42.7 (NCH2), 85.1, 124.2,
126.9, 128.2, 128.7, 128.8, 129.0, 134.5, 137.1, 140.4, 159.0
2-Benzyl-6-bromobenzo[d]isothiazol-3(2H)-one 1,1-dioxide
(N-benzyl-6-bromosaccharin) (12)
6-Bromosaccharin (11, 0.42 g, 1.6 mmol) was dissolved (C=O) ppm. – MS (CI+): m/z (%) = 400 (100) [M + H]+.
in dry DMF (10 mL), sodium hydride (80% in mineral oil, – C20H22BNO5S (399.3): calcd. C 60.16, H 5.55, N 3.51;
53 mg, 1.8 mmol) was gradually added, and the mixture was found C 60.02, H 5.39, N 3.42.
Unauthenticated
Download Date | 1/10/17 7:57 AM

S. Buck – G. Maas · 3,300-Bis(saccharin-6-ylmethyl)-1,10:30,100-terphenyl
1077
(2-Benzyl-1,1-dioxido-3-oxo-2,3-dihydrobenzo[d]isothiazol- – IR (KBr): ν = 3032 w, 2933 w, 1732 vs (C=O), 1600 m,
6-yl)boronic acid [(N-benzylsaccharin-6-yl)boronic acid]
(14)
1338 s, 1324 s, 1261 s, 1171 s, 698 m, 595 m, 518 m cm−1
.
1
– H NMR (CDCl3): δ = 4.22 (s, 4 H, ArCH2Ar), 4.89 (s,
4 H, NCH2), 7.16 (d, J = 8.1 Hz, 2 H), 7.28–7.36 (m, 6 H),
7.41–7.57 (m, 13 H), 7.65–7.67 (m, 2 H), 7.72–7.75 (m, 3
H), 7.95 (d, J = 8.1 Hz, 2 H) (all arom. H) ppm. – 13C NMR
(CDCl3): δ = 42.0, 42.6, 121.0, 125.3, 126.2, 126.4, 127.9,
128.1, 128.2, 128.61, 128.62, 129.3, 129.5, 134.5, 134.9,
138.1, 138.7, 141.3, 141.9, 149.7, 158.8 (C=O) ppm. – MS
(CI+): m/z (%) = 801 (100) [M]+. – C48H36N2O6S2 (800.9):
calcd. C 71.98, H 4.53, N 3.50; found C 71.79, H 4.63, N
3.45.
Method B: In a thick-walled Schlenk tube, boronic acid
14 (1.40 g, 2.6 mmol), bis(bromomethyl)terphenyl 9 (0.70 g,
1.7 mmol, contaminated with a small amount of tetrabro-
mide 10) and 2 M aqueous Na2CO3 (5.9 mL, 11.8 mmol)
were mixed with toluene (40 mL) and ethanol (2 mL).
The mixture was degassed and saturated with argon, then
Pd(PPh3)4 (0.290 g, 0.25 mmol, 9.6 mol-% based on 14)
was added, and the mixture was kept with stirring at 90 ◦C
overnight (a homogeneous phase was formed). After cooling
dichloromethane (30 mL) was added, the solution was ex-
tracted with 3 × 20 mL of water, and the organic phase was
dried with Na2SO4. After evaporation of the solvent, a foam
remained which was separated by column chromatography
on silica gel (140 g, elution with cyclohexane/ethyl acetate
(5/1)), yielding 1.00 g (75%) of 15 as an off-white solid.
Sodium periodate (NaIO4, 0.81 g, 3.8 mmol) and
boronic acid ester 13 (0.50 g, 1.3 mmol) were stirred in
acetone/water (3/1, 30 mL) until a homogeneous solution
was formed. After addition of 2 M hydrochloric acid
(0.4 mL), the solution was stirred overnight. The colorless
precipitate was filtered off with suction and washed with
a small amount of cold acetone. The solid was discarded,
and to the combined filtrates water was added until the
solution became turbid. It was then left overnight in an open
vessel (hood!) to allow acetone to evaporate. The formed
precipitate of colorless needles was collected and dried at
r. t./0.001 mbar for 1 h. Yield of 14: 0.38 g (96%), m. p.
180–181 ◦C. – IR (KBr): ν = 3553 s, 3358 br s, 3078 w,
2915 w, 1743 vs (C=O), 1453 m, 1427 s, 1350 vs, 1320
vs, 1285 vs, 1180 s, 1154 s, 1126 m, 1061 m, 958 m, 688
s, 599 m, 513 m cm−1. – 1H NMR (CD3OD): δ = 4.88
(s, 2 H, NCH2), 7.26–7.35 (m, 3 H, Hphenyl), 7.45 (d, J =
7.1 Hz, 2 H, Hphenyl), 8.01 (d, J = 3.8 Hz, 1 H, Haryl), 8.23
(d, J = 4.1 Hz, 1 H, Haryl), 8.29 (s, 1 H, Haryl) ppm. – 13C
NMR (CD3OD): δ = 43.3 (NCH2), 125.0, 126.7, 129.0,
129.1, 129.4, 129.6, 136.5, 138.5, 140.9, 160.6 (C=O) ppm.
– MS (CI+): m/z (%) = 274 (100) [M – B(OH)2 + 2 H]+,
184 (17) [M – B(OH)2 – Bn + 2 H]+. – C14H12BNO5S
(317.1): calcd. C 53.02, H 3.81, N 4.42; found C 52.99, H
3.82, N 4.40.
6,60-((1,10 : 30,100-Terphenyl)-3,300-diylbis(methylene))bis-
(benzo[d]isothiazol-3(2H)-one 1,1-dioxide [bis(saccharin-
6-ylmethyl)-1,10 : 30,100-terphenyl] (H2tpsac, 7)
6,60-((1,10 : 30,100-Terphenyl)-3,300-diylbis(methylene))bis(2-
benzylbenzo[d]isothiazol-3(2H)-one 1,1-dioxide [3,300-bis-
(N-benzylsaccharin-6-ylmethyl)-1,10 : 30,100-terphenyl] (15)
Benzyl-protected bis-saccharin 15 (0.20 g, 0.25 mmol),
Method A: A suspension of boronic acid ester 13 (0.50 g, ammonium formate (0.310 g, 5 mmol) and palladium on coal
1.3 mmol), bis(bromomethyl)terphenyl 9 (0.25 g, 0.6 mmol, (Pd/C 10%, 0.10 g, 0.09 mmol) in ethanol (30 mL) were kept
contaminated with a small amount of tetrabromide 10, see overnight with stirring at reflux temperature. The catalyst
above) and Cs2CO3 (0.86 g, 2.6 mmol) in THF (35 mL) was filtered off, the solvent was evaporated, and the residual
and water (4 mL) was prepared in a thick-walled Schlenk solid was suspended in 1 M aqueous HCl (30 mL) and ex-
tube, degassed, and saturated with argon. After addition of posed to ultrasonic irradiation for 5 min. The colorless jelly-
PdCl2(dppf)·CHCl3 (76 mg, 89 µmol, 14.8 mol-% based on like solid was filtered off with suction, washed with water
9), the mixture was kept with stirring at 80 ◦C overnight. Af- and dried for 2 h at 140 ◦C/0.001 mbar. A colorless solid
ter cooling the solvent was evaporated, the black residue was (0.13 g, 84%) was obtained. A DSC measurement indicated
dissolved in dichloromethane (50 mL), and this solution was a glass transition at Tg = 119 ◦C. – IR (KBr): ν = 3436
extracted with water (40 mL) to which 2 M aqueous HCl was br s, 3285 br s, 3057 br m, 2677 br w, 1735 vs (C=O),
added to facilitate the phase separation. The organic phase 1600 s, 1482 m, 1338 vs, 1248 s, 1171 vs, 1137 s, 1115 m,
was washed with water (2×40 mL) to remove traces of acid, 886 m, 788 m, 716 m, 597 m, 521 m cm−1. – 1H NMR
then dried with Na2SO4. A brown oil (0.53 g) was left af- (CDCl3/[D6]DMSO (9/1)): δ = 4.16 (s, 4 H, ArCH2Ar),
ter evaporation of the solvent, which was pre-purified by 7.12 (d, J = 7.6 Hz, 2 H), 7.35 (t, J = 7.6 Hz, 2 H), 7.41–7.48
passing it through a short silica gel column (elution with (m, 7 H), 7.60–7.66 (m, 5 H), 7.81 (d, J = 8.1 Hz, 2 H) (all
ethyl acetate). Further separation was achieved by column H-arom.) ppm. – 13C NMR (CDCl3/[D6]DMSO (9/1)): δ =
chromatography on silica gel [140 g, elution with cyclohex- 41.3 (ArCH2Ar), 120.2, 124.5, 125.3, 125.4, 125.69, 125.74,
ane/ethyl acetate (4/1] to yield 0.23 g (48%) of 15 as a color- 127.3, 127.6, 128.8, 128.9, 134.1, 138.6, 139.7, 140.7, 141.1,
less solid. – M. p. 138–144 ◦C (from THF/diisopropyl ether). 149.0, 160.2 (C=O) ppm. – MS (CI+): m/z (%) = 621 (100)
Unauthenticated
Download Date | 1/10/17 7:57 AM

1078
S. Buck – G. Maas · 3,300-Bis(saccharin-6-ylmethyl)-1,10:30,100-terphenyl
[M + H]+. – C34H24N2O6S2 (620.7): calcd. 65.79, H 3.90, stirred until a clear solution was formed. The solvent was
N 4.51; found C 65.68, H 4.02, N 4.50.
evaporated, and the residue was extracted while hot with two
portions of cyclohexane (1 mL for 6 µmol) in order to re-
move residual PPh3 (control by TLC). The yellow solid was
dried at 100 ◦C/0.001 mbar for 1 h. A 31P NMR spectrum
suggested the presence of complexes 19 and 20 in a 10 : 1
molar ratio. – Decomp. > 220 ◦C (heating rate 10 ◦C min−1).
– IR (KBr): ν = 3058 w, 2924 w, 2085 w (COax, 20), 2034 vs
(COeq), 1996 m (COeq), 1963 s (COeq), 1952 s (COeq), 1610
s (C=O, sac), 1571 s (C=O, sac), 1481 m, 1435 m, 1322
m, 1164 m, 695 m cm−1. – 1H NMR (CDCl3): δ = 3.85–
[Ru2(CO)5(µ,µ-tpsac)]2 (17)
Ru3(CO)12 (0.10 g, 0.16 mmol), H2tpsac (7, 0.15 g,
0.24 mmol) and dry toluene (30 mL) were placed in a thick-
walled Schlenk tube and kept with stirring at 130 ◦C
overnight. The solution was allowed to come to r. t., and
petroleum ether (30 mL) was added. The formed yel-
low precipitate was isolated and stirred in refluxing cy-
clohexane for 1 h. The solvent was evaporated, and the
residue was dried at 150 ◦C/0.001 mbar. A light-brown
solid (0.12 mg) was obtained, which still contained some
toluene that could not be removed even after longer dry-
ing at 150 ◦C/0.001 mbar. The complex decomposed above
380 ◦C (heating rate 10 ◦C min−1). NMR spectra indicate the
presence of two or more species. – IR (KBr): ν = 2926 w,
2851 w, 2096 s (COax), 2040 vs (COeq), 2013 vs (COeq),
1946 s (COeq), 1614 s (C=O, sac), 1577 s (C=O, sac),
4.09 (m, 4 H, CH2, 19 + 20), 6.87–7.77 (m, 52 H, Haryl
,
19 + 20) ppm. – 31P NMR (CDCl3): δ = 14.4 (19), 23.6
(20) ppm.
When complex 18 was allowed to react with two molar
equivalents of triphenylphosphane in CDCl3 solution (NMR
tube), complex 19 was formed almost exclusively, with only
traces of 20 detectable. 31P NMR: δ = 14.4 (19), 22.3
(slightly different from value given above for 20).
1376 m, 1322 m, 1163 s, 959 m cm−1. – 1H NMR (CDCl3, X-Ray structure determination of
325 K): δ = 3.99–4.20 (m, 8 H, CH2), 7.06–7.72 (m, 36 [Ru2(CO)4(PPh3)2(µ,µ-tpsac)] (19)
H, Haryl) ppm. – 13C NMR (CDCl3, 325 K): δ = 42.1–
42.2, 120.8–122.4, 124.2–129.4, 133.8–134.9, 138.6–139.2,
140.8–143.3, 148.4–148.6, 172.0, 175.5, 176.2, 178.5, 179.4,
194.1 – 199.3 ppm.
Suitable yellow crystals were obtained by slow evap-
oration of a toluene–dichloromethane solution at 7 ◦C.
Table 2. Crystal structure data for [Ru2(CO)4(PPh3)2(µ,µ-
tpsac)] (19).
[Ru2(CO)4(µ,µ-tpsac)]n (18)
In a round-bottom flask fitted with a reflux condenser,
complex 17 (55 mg) was heated for 4 d in toluene at
109 ◦C (50 mL). After cooling and evaporation of the sol-
vent in vacuo, the residue was dried at 150 ◦C/0.001 mbar
for 1 h. A greenish-grey solid of complex 18 was left
(47 mg, 45% yield based on Ru3(CO)12), which turned
yellow in contact with toluene or dichloromethane. De-
comp. > 220 ◦C (heating rate 10 ◦C min−1). – IR (KBr):
ν = 3059 w, 2926 w, 2046 vs (COeq), 1995 s (COeq),
1963 vs (COeq), 1614 s (C=O, sac), 1577 s (C=O, sac),
1311 m, 1156 s, 957 m cm−1. – The NMR spectra indi-
cate the presence of more than one species. – 1H NMR
([D6]DMSO, 350 K): δ = 4.05–4.30 (m, 4 H, CH2), 7.05–
8.02 (m, 18 H, CHar) ppm. – 13C NMR ([D6]DMSO, 350 K):
δ = 40.4, 40.5, 119.9–121.1, 123.6–128.9, 133.8–134.2,
139.7–141.6, 148.8–149.3, 175.9–177.2, 197.0 – 200.1 ppm.
– C38H22N2O10Ru2S2 (932.9): C 48.93, H 2.38, N 3.00;
found C 48.79, H 2.38, N 2.84.
Formula
Mr
Crystal size, mm3
Crystal system
Space group
C74H52N2O10P2Ru2S2
1457.38
0.23×0.23×0.19
monoclinic
C2/c
18.232(5)
20.782(5)
18.252(4)
90
118.89(3)
90
˚
a, A
˚
b, A
˚
c, A
α, deg
β, deg
γ, deg
3
˚
V, A
6055(2)
4
1.60
6.9
Z
Dcalcd, g cm−3
µ(MoKα ), cm−1
F(000), e
2960
hkl range
θ range, deg
Refl. measured/unique/Rint
Param. refined/restraints
R(F)/wR(F2)a (I > 2σ(I))
R(F)/wR(F2)a (all reflexions)
GoF (F2)b
±21, ±24, ±21
2.34–24.41
23 399/4955/0.1003
416/0
0.0510/0.1103
0.0928/0.1223
0.876
[Ru2(CO)4(PPh3)2(µ,µ-tpsac)] (19) and
[Ru2(CO)5(PPh3)(µ,µ-tpsac)] (20)
−3
˚
∆ρfin (max/min), e A
1.26/−0.39
a
R(F) = ||F | − |F ||/ |F |; wR(F2) = [ (w(F2 − F2)2)/
∑
;
∑
∑
A mixture of complex 17 (1 equiv.), triphenylphosphane
(2 equiv.) and dichloromethane (1 mL for 8 µmol) was
o
c
o
o
c
.
w(F2)2]1/2
GoF = [ w(|F |−|F| )2/(Nobs −Nparam)]1/2
b
∑
∑
o
c
o
Unauthenticated
Download Date | 1/10/17 7:57 AM

S. Buck – G. Maas · 3,300-Bis(saccharin-6-ylmethyl)-1,10:30,100-terphenyl
1079
Data collection was performed at 190 K on an image-plate for structure solution and refinement: SHELX-97 [35, 36];
diffractometer (Stoe IPDS) using monochromated MoKα
molecule plot: ORTEP-3 [37]. Further details are provided
˚
radiation (λ = 0.71073A). The structure was solved by in Table 2.
Direct Methods and refined (F2 values) using a full-
CCDC 882161 contains the supplementary crystallo-
matrix least-squares method. Hydrogen atom positions were graphic data for this paper. These data can be obtained free
calculated geometrically and treated as riding on their of charge from The Cambridge Crystallographic Data Centre
bond neighbors in the refinement procedure. Software via www.ccdc.cam.ac.uk/data request/cif.
[1] M. P. Doyle, M. A. McKervey, T. Ye, Modern Catalytic [21] C. G. Espino, K. W. Fiori, M. Kim, J. Du Bois, J. Am.
Methods for Organic Synthesis with Diazo Compounds,
John Wiley & Sons, New York, NY 1998.
[2] J. P. Snyder, A. Padwa, T. Stengel, A. J. Arduengo III,
Chem. Soc. 2004, 126, 15378 – 15379.
[22] D. N. Zalatan, J. Du Bois, J. Am. Chem. Soc. 2009, 131,
7558 – 7559.
A. Jockisch, H.-J. Kim, J. Am. Chem. Soc. 2001, 123, [23] B. H. Brodsky, J. Du Bois, Chem. Commun. 2006,
11318 – 11319. 4715 – 4717.
[3] L. Scha¨ffler, S. Buck, G. Maas, Inorg. Chim. Acta 2008, [24] F. Gonza´lez-Bobes, M. D. B. Fenster, S. Kiau, L. Kolla,
361, 109 – 122.
S. Kolotuchin, M. Soumeillant, Adv. Synth. Catal.
[4] D. T. Nowlan III, T. M. Gregg, H. M. L. Davies, D. A.
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