Convenient synthesis of anionic dinuclear ruthenium(II) complexes [NR2H2][{RuCl(diphosphine)}2(μ-Cl) 3] [diphosphine = 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl, 2,2′-bis(di(p-tolyl)phosphino)-1,1′-binaphthyl, and 1,2-bis(diphenylphosphino)benzene]:

Article abstract of DOI:10.1016/S0022-328X(00)00192-3

We report a practical one-pot synthesis of dialkylammonium salts of anionic dinuclear ruthenium complexes having chelating diphosphine ligands, BINAPs and DPB, with formula of [NEt₂H₂][{RuCl(diphosphine)}₂(μ-Cl) ₃] [2a: diphosphine = 2,2′-bis-(diphenylphosphino)-1,1′-binaphthyl; 6a: 2,2′-bis(di(p-tolyl)phosphino)-1,1′-binaphthyl; 8a: 1,2-bis(diphenylphosphino)benzene]. Treatment of cationic ruthenium complexes, [RuCl(η⁶-p-cymene)(diphosphine)]Cl (4) with a slight excess of NEt₂H₂Cl (5a) afforded 2a, 6a, and 8a in quantitative yields. Similar reactions with various dialkylammonium salts 5b-f gave the corresponding salts, [NR₂H₂][{RuCl(diphosphine)}₂(μ-Cl) ₃]. A one-pot mixture of BINAP or its derivative, [RuCl₂(η⁶-arene)]₂, and NR₂H₂Cl produced salts of the anionic dinuclear complexes which can be applied as catalysts for the asymmetric hydrogenation of ketonic substrates such as acetol and methyl acetoacetate with high activity and high enantioselectivity. The anionic face-sharing bioctahedral structure of these complexes was confirmed by the X-ray analysis of 8a, which has two hydrogen bonds between two NH of the diethylammonium cation and two terminal chloro-ligands.

Full text of DOI:10.1016/S0022-328X(00)00192-3

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 607 (2000) 51–56
Convenient synthesis of anionic dinuclear ruthenium(II) complexes
[NR2H2][{RuCl(diphosphine)}2(m-Cl)3]
[diphosphine=2,2%-bis(diphenylphosphino)-1,1%-binaphthyl,
2,2%-bis(di(p-tolyl)phosphino)-1,1%-binaphthyl, and
1,2-bis(diphenylphosphino)benzene]: crystal structure of
[NEt2H2][{RuCl(1,2-bis(diphenylphosphino)benzene)}2(m-Cl)3]
Kazushi Mashima *, Tomoko Nakamura, Yutaka Matsuo, Kazuhide Tani
Department of Chemistry, Graduate School of Engineering Science, Osaka Uni6ersity, Toyonaka, Osaka 560-8531, Japan
Received 23 February 2000; received in revised form 17 March 2000
Dedicated to Professor Martin A. Bennett on the occasion of his retirement from the Australian National University and for his contribution
to organometallic and inorganic chemistry.
Abstract
We report a practical one-pot synthesis of dialkylammonium salts of anionic dinuclear ruthenium complexes having chelating
diphosphine ligands, BINAPs and DPB, with formula of [NEt2H2][{RuCl(diphosphine)}2(m-Cl)3] [2a: diphosphine=2,2%-bis-
(diphenylphosphino)-1,1%-binaphthyl; 6a: 2,2%-bis(di(p-tolyl)phosphino)-1,1%-binaphthyl; 8a: 1,2-bis(diphenylphosphino)benzene].
Treatment of cationic ruthenium complexes, [RuCl(h6-p-cymene)(diphosphine)]Cl (4) with a slight excess of NEt2H2Cl (5a)
afforded 2a, 6a, and 8a in quantitative yields. Similar reactions with various dialkylammonium salts 5b–f gave the corresponding
salts, [NR2H2][{RuCl(diphosphine)}2(m-Cl)3]. A one-pot mixture of BINAP or its derivative, [RuCl2(h6-arene)]2, and NR2H2Cl
produced salts of the anionic dinuclear complexes which can be applied as catalysts for the asymmetric hydrogenation of ketonic
substrates such as acetol and methyl acetoacetate with high activity and high enantioselectivity. The anionic face-sharing
bioctahedral structure of these complexes was confirmed by the X-ray analysis of 8a, which has two hydrogen bonds between two
NH of the diethylammonium cation and two terminal chloro-ligands. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: Ruthenium; Anionic dinuclear; Chelating diphosphines
[13]. Despite the outstanding performance of 1 in asym-
metric hydrogenation, the structure of 1 had not been
revealed until we and another group reported this com-
plex to be an anionic dinuclear complex, [NEt2H2]-
[{RuCl(BINAP)}2(m-Cl)3] (2a), on the basis of the crys-
tallographic study of [NEt2H2][{RuCl((R)-p-MeO-BI-
NAP)}2(m-Cl)3] [(R)-3a] [p-MeO-BINAP=2,2%-bis-
(di(p-methoxyphenyl)phosphino)-1,1%-binaphthyl] [14]
and ESIMS of 2a [15]. The original synthetic method
starting from a mixture of [RuCl2(cod)]n, NEt3, and
BINAP gave 2a with severe contamination by the hy-
dride complex, [RuHCl(BINAP)2], which not only re-
duced the chemical yield of 2a but also hampered its
1. Introduction
Recently various mononuclear ruthenium(II) com-
plexes bearing chiral diphosphines such as BINAP (BI-
NAP=2,2% - bis(diphenylphosphino) - 1,1% - binaphthyl)
have extensively been applied as catalyst precursors for
the asymmetric hydrogenation of olefins and ketones
[1–12]. The first dinuclear Ru(II)ꢀBINAP complex was
prepared and formulated as Ru2Cl4(BINAP)2·NEt3 (1)
* Corresponding author. Tel.: +81-6-68506247; fax: +81-6-
68506296.
E-mail address: mashima@chem.es.osaka-u.ac.jp (K. Mashima).
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(00)00192-3

52
K. Mashima et al. / Journal of Organometallic Chemistry 607 (2000) 51–56
purification [13,14,16]. Thus, a more convenient synthe-
sis of the anionic complex 2a has been required. Herein
we report a convenient one-pot synthesis of 2a and its
derivatives with high purity and high chemical yield by
treating [RuCl2(h6-arene)]2 with BINAP and NR2H2Cl.
James and co-workers have previously reported that the
addition of NEt2H2Cl to the five-coordinate complex
[RuCl2(BINAP)(PPh3)] afforded complex 2a [17].
tions using ethylammonium chloride NEtH3Cl or tri-
ethylammonium chloride NEt3HCl also afforded the
corresponding complexes, whose 31P{1H}-NMR spectra
displayed typical ABq signals [l 51.1 and 52.9 (40 Hz)
for the NEtH3Cl reaction and l 50.9 and 52.8 (38 Hz)
for NEt3HCl], while the reaction using NH4Cl did not.
Reactions of [RuCl(h6-p-cymene)((S)-p-TolBINAP)]Cl
[(S)-4b] [p-TolBINAP=2,2%-bis(di(p-tolyl)phosphino)-
1,1%-binaphthyl] [4] with 5a–c afforded the correspond-
ing anionic dinuclear complexes, [NR2H2][{RuCl((S)-
p-TolBINAP)}2(m-Cl)3] [(S)-6, a: R=Et; b: R=Me; c:
R=iPr].
2. Results and discussion
Treatment of a cationic ruthenium complex, [RuCl-
(h6-p-cymene)((S)-BINAP)]Cl [(S)-4a] [4] with a slight
excess of NEt2H2Cl (5a) in THF for 6 h afforded
orange (S)-2a in quantitative yield after removal of the
solvent and washing. The product contained a small
amount of 5a. Similar reactions of (S)-4a with various
dialkylammonium salts 5b–f resulted in the quantita-
tive formation of (S)-2b–f. The 31P{1H}-NMR spectra
of these complexes showed almost the same ABq signal
(l 51–57) with the same coupling constant (38 Hz) due
to the chirality of the BINAP ligand, indicating that
these complexes have the same anionic dinuclear ge-
ometry as 2a and 3a (Table 1). In the case of much
bulkier dialkylammonium salts such as 5c–e, the prod-
ucts were obtained with a slight contamination by the
unidentified compound that showed another ABq signal
at l 53.9 and 59.3 with a coupling constant of 40 Hz in
the 31P{1H}-NMR spectra of the products. The reac-
As the cationic mononuclear rutheniumꢀBINAP
complex 4b has been prepared by simply mixing
[RuCl2(h6-p-cymene)]2 (7b) and p-TolBINAP [4], the
one-pot mixture of (S)-p-TolBINAP, 7b, and
NEt2H2Cl in toluene produced (S)-6a in quantitative
yield with high purity as expected. Similarly, (R)-2b can
be derived from the mixture of (R)-BINAP, [RuCl2(h6-
benzene)]2 (7a), and NMe2H2Cl. These anionic dinu-
clear ruthenium(II) complexes (R)-2b and (S)-6a
obtained in a one-pot manner can be used for asymmet-
ric hydrogenation of various organic substrates such as
acetol and methyl acetoacetate not only with high
enantioselectivity but also with increased catalytic ac-
tivity, giving (R)-1,2-propanediol (93% ee by (R)-2b)
and (S)-methyl 3-hydroxybutanoate (99% ee by (S)-6a).
All attempts to crystallize these anionic dinuclear
complexes 2 and 6 resulted in the formation of brittle
solids or jelly semisolids, not suitable for X-ray analy-
sis. In the case of 1,2-bis(diphenylphosphino)benzene
(DPB), a peraryl chelating diphosphine ligand, we ob-
Table 1
31P{1H}-NMR spectral data of anionic dinuclear ruthenium com-
plexes bearing BINAP or its derivatives a
Complex
Chemical shift (l)
Coupling constant (Hz)
2a
51.8
52.3
51.5
51.8
51.8
52.1
51.5
49.5
49.5
49.9
49.6
54.4
38
56.5
52.8
55.9
55.9
56.5
52.8
52.0
51.0
49.0
53.3
38 in CD2Cl2 [16])
2b
2c
2d
2e
2f
3a
6a
6b
6c
38
38
38
38
38
38
38
38
38
a Measured in CDCl3.

K. Mashima et al. / Journal of Organometallic Chemistry 607 (2000) 51–56
53
chlorine atom has a shorter RuꢀCl distance (2.417(2)–
,
,
2.448(2) A) than those (2.479(2)–2.515(2) A) of the
bridging chlorides trans to phosphorus atoms due to
the weaker trans effect of the Cl ligand compared with
that of the phosphine ligand. Each DPB ligand forms a
puckered five-membered-chelate.
The presence of two hydrogen bonds between the
two NH of the diethylammonium cation and two termi-
nal chloro-ligands, Cl(4) and Cl(5), is revealed by the
,
short distances NꢀCl(4) [3.250(9) A for molecule I and
,
,
3.290(9) A for molecule II] and NꢀCl(5) [3.346(9) A for
,
molecule I and 3.224(10) A for molecule II]. It is
noteworthy that the diethylammonium chloride plays
Table 2
Fig. 1. ORTEP drawing of one of the two crystallographically indepen-
dent ion pairs of 8a with the numbering scheme. Hydrogen atoms are
omitted for clarity.
,
Selected bond distances (A) and angles (°) of 8a
Molecule I
Molecule II
tained crystals suitable for an X-ray crystallographic
study. Thus, 8a was prepared by the reaction of
[RuCl(h6-p-cymene)(DPB)]Cl (4c) [18] with 5a in THF.
The 31P{1H}-NMR spectrum of 8a displayed a singlet
at l 79.7, downfield-shifted compared with that (l 64.2)
of 4c.
Ru(1)···Ru(2)
Ru(1)ꢀCl(1)
Ru(1)ꢀCl(2)
Ru(1)ꢀCl(3)
Ru(1)ꢀCl(4)
Ru(1)ꢀP(1)
Ru(1)ꢀP(2)
Ru(2)ꢀCl(1)
Ru(2)ꢀCl(2)
Ru(2)ꢀCl(3)
Ru(2)ꢀCl(5)
Ru(2)ꢀP(3)
Ru(2)ꢀP(4)
3.271(1)
2.515(2)
2.433(2)
2.479(2)
2.411(2)
2.234(2)
2.222(2)
2.508(2)
2.417(2)
2.485(2)
2.416(2)
2.231(2)
2.242(2)
3.279(1)
2.493(2)
2.437(2)
2.479(2)
2.412(2)
2.239(2)
2.231(2)
2.501(2)
2.448(2)
2.506(2)
2.417(2)
2.240(2)
2.235(2)
Cl(1)ꢀRu(1)ꢀCl(2)
Cl(1)ꢀRu(1)ꢀCl(3)
Cl(1)ꢀRu(1)ꢀCl(4)
Cl(1)ꢀRu(1)ꢀP(1)
Cl(1)ꢀRu(1)ꢀP(2)
Cl(2)ꢀRu(1)ꢀCl(3)
Cl(2)ꢀRu(1)ꢀCl(4)
Cl(2)ꢀRu(1)ꢀP(1)
Cl(2)ꢀRu(1)ꢀP(2)
Cl(3)ꢀRu(1)ꢀCl(4)
Cl(3)ꢀRu(1)ꢀP(1)
Cl(3)ꢀRu(1)ꢀP(2)
Cl(4)ꢀRu(1)ꢀP(1)
Cl(4)ꢀRu(1)ꢀP(2)
P(1)ꢀRu(1)ꢀP(2)
Cl(1)ꢀRu(2)ꢀCl(2)
Cl(1)ꢀRu(2)ꢀCl(3)
Cl(1)ꢀRu(2)ꢀCl(5)
Cl(1)ꢀRu(2)ꢀP(3)
Cl(1)ꢀRu(2)ꢀP(4)
Cl(2)ꢀRu(2)ꢀCl(3)
Cl(2)ꢀRu(2)ꢀCl(5)
Cl(2)ꢀRu(2)ꢀP(3)
Cl(2)ꢀRu(2)ꢀP(4)
Cl(3)ꢀRu(2)ꢀCl(5)
Cl(3)ꢀRu(2)ꢀP(3)
Cl(3)ꢀRu(2)ꢀP(4)
Cl(5)ꢀRu(2)ꢀP(3)
Cl(5)ꢀRu(2)ꢀP(4)
P(3)ꢀRu(2)ꢀP(4)
79.10(7)
83.11(7)
91.05(7)
176.18(8)
95.63(8)
80.41(7)
165.96(8)
104.48(8)
99.20(8)
88.57(8)
96.08(8)
178.72(8)
85.20(8)
91.64(8)
85.20(9)
79.56(7)
83.14(7)
90.82(8)
176.48(8)
97.83(8)
80.60(7)
166.86(8)
100.15(8)
100.70(8)
89.44(8)
96.39(8)
178.49(9)
89.40(8)
89.39(8)
82.63(8)
80.51(8)
84.18(7)
90.81(9)
94.75(8)
177.31(9)
78.96(8)
164.77(8)
103.84(9)
100.51(9)
87.78(9)
176.83(9)
98.45(8)
89.25(9)
88.73(9)
82.59(9)
80.14(8)
83.48(8)
88.75(8)
98.29(9)
176.52(9)
78.24(8)
166.10(9)
99.85(9)
102.70(8)
92.30(8)
177.19(9)
95.08(9)
89.93(9)
88.14(8)
83.3(1)
Two crystallographically independent ion pairs of 8a
crystallized in a triclinic system and one of them is
shown in Fig. 1. Selected interatomic distances and
angles are listed in Table 2. This complex has an
anionic triply chloride-bridged dinuclear [(RuCl)(m2-
Cl)3(RuCl)]-core. The distance between the two adja-
,
cent ruthenium atoms, Ru(1)ꢀRu(2) [3.271(1) A for
,
molecule I and 3.279(1) A for molecule II], is compara-
,
ble to that (3.25–3.35 A) reported for trichloro bridged
Ru2 complexes such as [Ru2Cl5(CHIRAPHOS)2] [19],
[Ru2Cl5(PR3)4] [20,21], [Ru2Cl4(CS)(PPh3)4] [22],
[Ru2Cl4(DMSO)(DPPB)2] (DPPB=bis(diphenylphos-
phino)butane) [23], [Ru2Cl4(h2-H2)(DPPB)2] [17],
[Ru2Cl3(PR3)6]+ [20,21,24], and (R)-3a [14], being well
outside the range (2.28–2.95 A) expected for a RuꢀRu
single bond [20,21,25–28]. Furthermore, it is of interest
that an isoelectronic carbonyl complex, [{RuCl(CO)2}2-
(m-Cl)3]− also adopts the face-sharing bioctahedral
structure [29].
Each ruthenium center adopts a pseudo-octahedral
structure, as expected for d6 Ru(II), defined by the two
phosphorus atoms of the DPB ligand and four chlorine
atoms. The bridging chloride Cl(2) trans to a terminal

54
K. Mashima et al. / Journal of Organometallic Chemistry 607 (2000) 51–56
an important role in the formation of the anionic
dinuclear structure through the two NH···Cl hydrogen
bonds. We have already reported that the release of the
arene ligand bound to the ruthenium of 4 led to the
(83 mg, 1.0 mmol) placed in a 250 ml Schlenk tube was
added dry 1,4-dioxane (75 ml). This reddish suspension
was heated at 50°C with stirring for 2 h, then refluxed
with stirring for 12 h. The resulting clear red–brown
solution was cooled to room temperature (r.t.), and the
solvent was removed under vacuum to leave brown
solids of (R)-2b in quantitative yield.
formation of
a
cationic trinuclear complex
[Ru3Cl5(BINAP)3]+, which was found to be inert in
catalytic hydrogenation owing to the lack of a coordi-
nation site available for substrates and/or hydrogen
[30]. The anionic dinuclear complexes, on the other
hand, can readily generate a coordination site by elimi-
nating the dialkylammonium chloride, and hence
showed high catalyst performance. Dinuclear com-
plexes, in fact, have been previously reported to cata-
lyze hydrogenation [31,32].
3.4. Asymmetric hydrogenation of 2-oxo-1-propanol
(acetol) using (R)-2b prepared in a one-pot manner
The above catalyst (R)-2b (83.5 mg, 0.05 mmol) was
introduced into a 200 ml stainless steel autoclave. The
atmosphere was replaced with nitrogen, then substrate
(14.82 g, 200 mmol, S/C=4000) and methanol (30 ml)
were added. The nitrogen atmosphere was replaced
with hydrogen (1 Mpa) and then the mixture was
stirred at 65°C for 16 h. The reaction product, (R)-1,2-
propanediol (quantitative yield), was analyzed by
means of gas chromatography (column: a-DEX 120
(Supelco Inc.)) and 92.8% ee was found.
In conclusion, we have demonstrated a practical one-
pot synthesis of anionic dinuclear ruthenium complexes
having chelating diphosphine ligands, BINAPs and
DPB. The BINAP complexes showed high catalytic
activity in the asymmetric hydrogenation of ketonic
substrates. This synthetic procedure requires no difficult
manipulations.
3.5. One-pot synthesis of (S)-6a
3. Experimental
To a mixture of [RuCl2(h6-p-cymene)]2 (7b, 0.31 g,
0.5 mmol), (S)-p-TolBINAP (0.68 g, 1.0 mmol), and
NEt2H2Cl (0.11 g, 1.0 mmol) placed in a 250 ml
Schlenk tube was added dry toluene (50 ml). The
reddish suspension was heated at 50°C with stirring for
2 h, and then refluxed with stirring for 12 h. After the
resulting clear red–brown solution was cooled to r.t.,
all volatiles were removed under vacuum to leave
brown solids in quantitative yield.
3.1. General
All manipulations involving air- and moisture-sensi-
tive organometallic compounds were carried out using
standard Schlenk techniques under argon. Mono-
nuclear cationic ruthenium complexes [RuCl(h6-p-
cymene)((S)-BINAP)]Cl (4a) [4], [RuCl(h6-p-cymene)-
((S)-p-TolBINAP)]Cl (4b) [4], and [RuCl(h6-p-
cymene)(DPB)]Cl (4c) [18] were prepared according to
1
3.6. Asymmetric hydrogenation of methyl acetoacetate
using (S)-6a prepared in a one-pot manner
the literature procedures. H (270 MHz and 300 MHz)
and 31P(109.25 and 121.49 MHz)-NMR spectra were
measured on a JEOL JNM-GSX-270 spectrometer and
a Varian MERCURY 300 spectrometer. Elemental
analyses were performed on a Perkin–Elmer 2400 mi-
croanalyzer. All melting points were measured in sealed
tubes and were not corrected.
The above catalyst (S)-6a (18.1 mg, 0.01 mmol) was
introduced into a 200 ml stainless steel autoclave. The
atmosphere was replaced with nitrogen, then substrate
(11.61 g, 100 mmol, S/C=10 000) and methanol (20
ml) were added. The nitrogen atmosphere was replaced
with hydrogen (3 Mpa) and then the mixture was
stirred at 50°C for 12 h. The reaction product, (S)-
methyl 3-hydroxybutanoate (quantitative yield), was
analyzed by means of gas chromatography (column:
Chiraldex B-TA (ASTEC Inc.)) and 99.2% ee was
found.
3.2. Preparation of 2a
A solution of (S)-4a (29.4 mg, 0.032 mmol) and
NEt2H2Cl (3.7 mg, 0.032 mmol) in THF (15 ml) was
heated for 6 h to give an orange solution, from which
complex (S)-2a was obtained in quantitative yield after
removal of the solvent and washing. Similar reactions
gave complexes 2b–f and 6a–c, which were character-
ized by their 31P{1H}-NMR spectra.
3.7. Preparation of 8a
A reaction mixture containing 4c (180 mg, 0.259
mmol) and NEt2H2Cl (56.7 mmol, 0.517 mmol) in THF
(60 ml) was heated to reflux for a period of 9 h, giving
an orange–yellow solution. All volatiles were removed
under reduced pressure. The resulting residue was re-
3.3. One-pot synthesis of (R)-2b
To a mixture of [RuCl2(h6-benzene)]2 (7a, 0.25 g, 0.5
mmol), (R)-BINAP (0.63 g, 1.0 mmol), and NMe2H2Cl

K. Mashima et al. / Journal of Organometallic Chemistry 607 (2000) 51–56
55
Table 3
reflections. An empirical absorption correction was ap-
plied on the basis of azimuthal scans. The data was
corrected for Lorentz and polarization effects.
Crystal and refinement data for 8a
Formula
C65H62NCl7P4Ru2
The structure of complex 8a was solved by a direct
method (SHELXS-86) [33] and refined by the full-matrix
least-squares method. Measured non-equivalent reflec-
tions were used for the structure determination. In the
subsequent refinement, the function Sꢀ(ꢀFoꢀ−ꢀFcꢀ)2 was
minimized, where ꢀFoꢀ and ꢀFcꢀ are the observed and
calculated structure factor amplitudes, respectively. The
agreement indices are defined as R1=S(ꢀꢀFoꢀ−ꢀFcꢀꢀ)/
SꢀFoꢀ and wR2=[Sꢀ(F2o−Fc2)2/S(ꢀF4o)]1/2. The posi-
tions of all non-hydrogen atoms for all complexes were
found from a difference Fourier electron density map
and refined anisotropically. All hydrogen atoms were
Formula weight
Crystal system
Space group
1431.618
Triclinic
(
P1 (c2)
,
a (A)
15.700(4)
33.96(1)
13.137(4)
98.48(3)
104.04(2)
87.74(2)
4
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
Z
3
,
V (A )
6720(3)
1.415
Mo–Ka
+h, +k, 9l
0.27×0.20×0.17
8.61
Dcalc (g cm−3
)
Radiation
Reflections measured
Crystal size (mm)
Absorption coefficient (cm−1
Scan mode
Temperature (°C)
2q max (°)
,
placed in calculated positions (CꢀH=0.95 A) and kept
)
fixed. All calculations were performed using the
ꢀ
TEXSAN crystallographic software package.
23
55.1
Data collected
31 990
Unique data
30 851 (Rint=0.072)
30 837
1423
Acknowledgements
No. of observations
No. of variables
R [I\3|(I)]
We thank Dr N. Sayo (Takasago International
Corp., Japan) for his helpful discussions. This work
was financially supported by a Grant-in-Aid for Scien-
tific Research on Priority Area (no. 283, ‘Innovative
Synthetic Reactions’) from the Ministry of Education,
Science and Culture, Japan. Y.M. is a research fellow
of the Japan Society for the Promotion of Science,
1998–2000.
0.064
Rw [I\3|(I)]
R1 (all data)
0.064
0.189
0.190
1.38
wR2 (all data)
Goodness-of-fit on F2
−3
,
Largest difference peak and hole (e A
)
2.28 and −1.91
crystallized from a mixture of dichloromethane (15 ml)
and hexane (15 ml). Orange–yellow crystals of 8a (87.4
mg, 47% yield) were obtained; m.p. 284–286 (dec.).
References
2
1H-NMR (270 MHz, CDCl3, 30°C): l 1.09 (t, JHH
=
7.3 Hz, 6H, ꢀCH2CH3), 2.92 (m, 4H, ꢀCH2CH3), 6.8–
7.7 (m, 48H, aromatic protons), 8.16 (broad s, 2H,
H2N). 31P{1H}-NMR (109 MHz, CDCl3, 30°C): l 79.7
(s). Elemental analyses showed that 8a crystallized with
free diethylammonium chloride, and thus did not give a
satisfactory result.
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