New Highly Stable Metallabenzenes
FULL PAPER
Table 3. Crystal data and structure refinement for 3’, 4, 6, and 7.
on an Elementar Analysen Syetem
GmbH Vario EL III instrument. Ab-
sorption and fluorescence spectra were
recorded on a Varian CARY-300 UV/
Vis spectrophotometer and a Hitachi
F-4500 fluorophotometer, respectively.
3’·2.5C2H4Cl2·0.25CH2Cl2
4
6·C2H4Cl2·3.5H2O
7·2H2O
formula
C
130.25H109.50B2Cl5.50N2O2P3Ru C59H45ClN2O2P2
C70H64Cl5NO4.50P3Ru C50H42ClNO3P2
Ru
Mr
2145.27
triclinic
P1
1012.43
monoclinic
P2/c
26.1400(12)
8.6146(3)
22.7498(11)
90
113.643(6)
90
4692.9(4)
4
1.433
0.507
2080
0.30ꢃ0.25ꢃ0.20
2.36–25.00
20664
1362.45
triclinic
802.24
crystal system
space group
a [ꢁ]
b [ꢁ]
c [ꢁ]
triclinic
[Ru
(C9H6NO)
[Ru{CHC(PPh3)CHC
(PPh3)2]Cl (1) (0.40 g, 0.30 mmol) and
8-hydroxyquinoline (65 mg,
A
N
ACHTUNGRTENUN(NG PPh3)CH}Cl-
¯
¯
¯
P1
P1
A
ACHTUNGTRENNUNG
13.9628(4)
17.3434(4)
25.0208(7)
72.775(2)
80.096(2)
84.007(2)
5691.9(3)
2
13.606(3)
14.287(3)
19.144(4)
86.08(3)
69.60(3)
82.76(3)
3458.9(12)
2
1.308
0.536
1402
0.42ꢃ0.25ꢃ0.20
3.02–25.00
44057
9.1489(18)
14.506(3)
15.494(3)
98.60(3)
90.66(3)
96.77(3)
2018.1(7)
2
1.320
0.220
840
0.20ꢃ0.15ꢃ0.10
3.21–25.00
15858
A
R
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
a [8]
b [8]
0.45 mmol) in CH2Cl2 (10 mL) was
stirred at room temperature for about
g [8]
2 h to give
a brown solution. The
V [ꢁ3]
Z
volume of the mixture was reduced to
ca. 2 mL under vacuum and was puri-
fied by column chromatography (neu-
tral alumina, acetone/methanol 6:1) to
1calcd [gcmÀ3
]
1.252
0.361
2227
m [mmÀ1
(000)
]
F
N
give complex
(0.21 g, 53%). 1H NMR (300.1 MHz,
CDCl3): d=16.8 (dd, (P,H)=15.0,
7.8 Hz, 1H, RuCH), 16.4 (dd, J(P,H)=
2 as a brown solid
crystal size [mm3] 0.50ꢃ0.40ꢃ0.35
q range [8]
2.29–25.00
51149
20020
JACHTUNGTRENNUNG
reflns collected
independent
reflns
ACHTUNGTRENNUNG
8251
12147
7091
17.7, 7.8 Hz, 1H, RuCH), 8.2–6.6 ppm
(m, 52H, PPh3, C9H6NO, RuCHC-
observed reflns
12511
4489
10871
4513
AHCTUNGTRENNUNG
(PPh3)CH); 31P{1H} NMR (202.5 MHz,
A
CDCl3): d=36.4 (RuPPh3), 18.6
(CPPh3), 18.4 ppm (CPPh3); 13C{1H}
NMR (125.8 MHz, CDCl3): d=294.1
(br, RuCH), 289.7 (br, RuCH), 145.5
data/restraints/
params
20020/163/1351
8251/132/598
12147/12/775
7091/0/515
GOF on F2
R1/wR2
1.000
0.856
1.001
0.0575/0.1902
1.001
0.0694/0.1654
0.0688/0.2128
0.0530/0.0785
(t,
(PPh3)CH), 168.1–109.4 (m, PPh3,
C9H6NO), 116.1 (dd, (P,C)=71.3,
13.5 Hz, RuCHC(PPh3)), 114.0 ppm
(dd, (P,C)=73.5, 11.3 Hz, RuCHC-
(PPh3)); elemental analysis calcd (%)
for C68H54NOP3Cl2Ru: 70.04,
4.67, N 1.20; found: C 70.28, H 5.15, N 1.36.
[(C9H6NO)Ru{CHC(PPh3)CHC(PPh3)C}(C9H6NO)
lution of [Ru{CHC(PPh3)CHC(PPh3)CH}Cl2A(PPh3)2]Cl (1) (0.20 g,
0.15 mmol) and 8-hydroxyquinoline (0.10 g, 0.75 mmol) in CH2Cl2 (5 mL)
was added to suspension of CH3COONa (0.12 g, 1.5 mmol) and
J
G
RuCHC-
A
AHCTUNGTRENNUNG
R1/wR2 (all data)
0.1095/0.2259
0.1094/0.0850
0.0628/0.1951
2.374/À0.534
0.1118/0.2027
1.401/À0.731
JACHTUNGTRENNUNG
largest peak/
2.368/À0.690
0.982/À1.090
hole [eꢁÀ3
]
AHCTUNGTRENNUNG
JACHTUNGTRENNUNG
AHCTUNGTRENNUNG
C
H
air atmosphere via the SNAr reaction. The ruthenabenzene 3
can tolerate weak alkali or weak acid in solution. Reaction
of 3 with NaOH or Na2CO3 gave a mixture of ruthenaben-
G
R
G
G
A
ACHTUNGTRENUN(NG PPh3)]Cl2 (3): A so-
A
U
G
CHTUNGTRENNUNG
À
zene complexes 4 and 5, presumably through a P C bond
a
cleavage of the metallacycle. In addition, 3 readily reacted
with HCl to yield ruthenabenzene 6. Thermal stability tests
demonstrated that these new species of metallabenzenes
have remarkable stability both in solid state and in solution
under air atmosphere. Especially, 4, 5 and 6 can be heated
at 1508C for at least five hours without appreciable decom-
position. Complexes 4 and 5 were found to be fluorescent in
solution and have similar spectral behaviors to those organic
multicyclic compounds. It suggested a degree of electron de-
localization within the metallacycle and the 8-hydroxyquino-
line ring, which accorded with the X-ray diffraction study.
CH3OH (1 mL). The reaction mixture was stirred at room temperature
for 24 h under an air atmosphere to give a green suspension. The solvent
was removed under vacuum and the residue was extracted with CH2Cl2
(3ꢃ5 mL). The volume of the filtrate was reduced to about 1 mL under
vacuum and was purified by column chromatography (neutral alumina,
acetone/methanol 20:1) to give complex 3 as a green solid (0.15 g, 76%).
1H NMR (500.2 MHz, CD2Cl2): d=15.9 (d,
RuCH), 8.8–6.3 (m, 58H, PPh3, C9H6NO, RuCHC
(dd, (P,H)=13.5, 18.5 Hz, 1H, RuCHC
(PPh3)CH); 13C{1H} NMR
(125.8 MHz, CD2Cl2): d=286.6 (br, RuCH), 273.9 (d, J(P,C)=13.8 Hz,
RuC), 154.6 (dd, J(P,C)=24.9, 17.5 Hz, RuCHC(PPh3)CH), 167.2–110.8
(m, PPh3, C9H6NO), 114.0 (dd, (P,C)=78.6, 12.1 Hz, (PPh3)),
103.9 ppm (dd, (P,C)=74.2, 11.3 Hz,
(PPh3)); 31P{1H} NMR
JACHTUNGTRENNUNG
AHCTUNGTRENNUNG
J
N
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
J
N
CACHTUNGTRENNUNG
J
N
CACHTUNGTRENNUNG
(202.5 MHz, CD2Cl2): d=31.7 (RuPPh3), 26.1 (CPPh3), 18.8 ppm
(CPPh3); elemental analysis calcd (%) for C77H59N2O2P3Cl2Ru: C 70.64,
H 4.54, N 2.14; found: C 70.67, H 4.76, N 1.96.
ACHNUTGERT[NGNUN (C9H6NO)RuACHTNUGTREG{UNNN CHCAHCTNUGRTENN(GU PPh3)CHCACHNUTTRGEG(NNUN PPh3)C}ACHUTNTGRENNGU(C9H6NO)ACHNUTGTREG(NNNU PPh3)]ACHTNUGTRENN(GUN BPh4)2 (3’):
Experimental Section
A solution of NaBPh4 (68.4 mg, 0.2 mmol) in CH3OH (0.5 mL) was
added slowly to a solution of complex 3 (0.1 g, 0.08 mmol) in CH3OH
(2 mL). The reaction mixture was stirred at room temperature for 5 min
to give a green suspension. The green solid was collected by filtration,
washed with CH3OH (2ꢃ3 mL), and then dried under vacuum (0.13 g,
88%). Elemental analysis calcd (%) for C125H99B2N2O2P3Ru: C 80.00, H
5.32, N 1.49; found: C 80.10, H 5.19, N 1.95.
General comments: All manipulations were carried out at room tempera-
ture under a nitrogen atmosphere using standard Schlenk techniques,
unless otherwise stated. The starting material [Ru
ACHUTGTNNERNUG{CHCCAHTUNGTREN(NUGN PPh3)CHC-
G
CHTUNGTRENNUNG
NMR experiments were performed on a Bruker AV-300 spectrometer
(1H 300.1 MHz; 13C 75.5 MHz; 31P 121.5 MHz), or a Bruker AV-500 spec-
trometer (1H 500.2 MHz; 13C 125.8 MHz; 31P 202.5 MHz). 1H and
13C NMR chemical shifts are relative to TMS, and 31P NMR chemical
shifts are relative to 85% H3PO4. Elemental analyses data were obtained
A
E
E
G
G
(4)
and
A
R
ACHTUNGTRENNUNG
Chem. Eur. J. 2011, 17, 4223 – 4231
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4229