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(400 MHz, CD
3
CN, 298 K): δ = 1.29 [d, JH,H = 7.6 Hz, 6 H, troscopy. C29
H
27ClF
3
N
3
Ru (611.06): calcd. C 57.00, H 4.45, N
CH(CH
5
7
3
)
2
], 2.17 (s, 3 H, CH
.54 (each d, JH,H = 5.6 Hz, 2ϫ 2 H, C
.38 (m, 6 H, ArH), 7.60 (s, 1 H, NH), 9.93 (br., 2 H, NH) ppm.
3
), 2.90 [m, 1 H, CH(CH
3
)
2
], 5.29,
6.88; found C 57.04, H 4.26, N 6.89.
6 4
H
), 7.20 (m, 6 H, ArH),
4
-chlorophenyl
6
Complex 6: Complex 6 was prepared from LH
0.343 mmol), NaOAc (28 mg, 0.341 mmol), and [(η -C H )-
10 14
2
(134 mg,
–1
2
–1
–3
+
Λ
m
(MeCN) = 18.5 Ω cm mol , (10 m). MS (ESI ): m/z = 627
+
2-chlorophenyl +
–
RuCl(μ-Cl)] (100 mg, 0.163 mmol) in methanol (10 mL) by follow-
[M – 3Cl] ; 365 [M + Na – LH
3
] . MS (ESI ): m/z =
2
+
2-chlorophenyl +
ing a procedure analogous to that described previously for the syn-
thesis of complex 4 (see Method 2) to afford 6 as orange crystals,
yield 83% (178 mg, 0.270 mmol), m.p. 188 °C (decomp.). IR (KBr):
6
66 [M – 3Cl + K] , 392 [LH
monomer of 3. C29 Ru·H
6.36, H 4.16, N 5.59; found C 46.29, H 4.39, N 5.28.
3
]
in which M is the
H
29Cl
6
N
3
2
O (733.35 + 18.02): calcd. C
4
–
1 1
ν˜ = 3297 (m, NH), 1591 (vs, C=N), 823 (m, C–Cl) cm . H NMR
Data for 4: M.p. 225–227 °C. IR (KBr): ν˜ = 3378 (m, NH), 1534 (400 MHz, CDCl , 298 K): δ = 1.21 [d, J
= 7.4 Hz, 6 H,
3
H,H
–1
1
(
vs, C=N), 752 (s, C–Cl) cm . H NMR (400 MHz, CDCl
98 K): δ = 1.17 [d, JH,H = 6.6 Hz, 6 H, CH(CH ], 2.08 (s, 3 H,
CH ), 2.70 [m, 1 H, CH(CH ], 5.20 (d, JH,H = 5.8 Hz, 2 H, C ), 5.86 (s, 1 H, NH), 6.71, 6.88 (each d, J
.48 (br., 2 H, C ), 5.99 (s, 1 H, NH), 6.57 (t, JH,H = 7.7 Hz, 1 7.07 (m, 8 H, ArH) ppm. C{ H} NMR (100.5 MHz, CDCl ,
H, ArH), 6.72 (t, JH,H = 7.2 Hz, 1 H, ArH), 6.89 (t, JH,H = 6.6 Hz,
3
,
3 2 3 3 2
CH(CH ) ], 2.21 (s, 3 H, CH ), 2.68 [m, 1 H, CH(CH ) ], 5.11 (d,
2
3
)
2
JH,H = 5.5 Hz, 2 H, C H ), 5.33 (d, J
= 6.1 Hz, 2 H, C H ),
H,H
= 9.2 Hz, 2ϫ 2 H, ArH),
6
4
H,H
6
4
3
3
)
2
6
H
4
1
3
1
5
6 4
H
3
298 K): δ = 19.2 (CH ), 22.5 [CH(CH ) ], 31.5 (CHMe ), 78.8, 80.9
3
3 2
2
2
7
H, ArH), 6.97 (d, JH,H = 8.0 Hz, 1 H, ArH), 7.05 (m, 3 H, ArH), (p-cymene ArCH), 98.1, 99.1 (p-cymene ArC), 121.6, 124.7, 127.9,
.23 (d, JH,H = 8.0 Hz, 2 H, ArH), 7.49 (br., 2 H, ArH) ppm. 128.4, 128.7, 128.9, 136.2, 145.1, 153.5 (ArC/ArCH and
1
3
1
C{ H} NMR (100.5 MHz, CDCl
3
, 298 K): δ = 18.7 (CH
3
), 22.5
29 27 4 3
C=N) ppm. C H Cl N Ru (660.43): calcd. C 52.74, H 4.12, N
[
CH(CH ], 31.0 (CHMe ), 78.8, 80.6 (p-cymene ArCH), 95.8,
3
)
2
2
6.36; found C 52.34, H 4.23, N 6.22.
1
1
00.2 (p-cymene ArC), 121.9, 122.5, 122.8, 124.6, 126.4, 127.3,
28.3, 129.4, 134.1, 143.7, 153.9 (ArC/ArCH and C=N) ppm.
4
-nitrophenyl
6
Complex 7: Complex 7 was obtained from LH
0
2
(138 mg,
.327 mmol), NaOAc (27 mg, 0.329 mmol), and [(η -C10H14)-
RuCl(μ-Cl)] (100 mg, 0.163 mmol) in methanol (10 mL) by follow-
2
ing a procedure analogous to that described for complex 4 (see
Method 2) with the exception being the reaction mixture was
heated at reflux for 24 h. Complex 7 was obtained as green crystals
Note: Only 11 carbon resonances were observed for the ArC/ArCH
and C=N carbons of the guanidinate ligand rather than the ex-
pected 13 peaks, presumably due to the overlapping of peaks. MS
+
+
(
(
6
ESI): m/z = 624 [M – Cl] , 625 [M + H– Cl] . C29
660.43): calcd. C 52.74, H 4.12, N 6.36; found C 52.38, H 4.45, N
.27.
4 3
H27Cl N Ru
from MeOH/CHCl
3% (97 mg, 0.120 mmol), m.p. 260 °C (decomp.). IR (KBr): ν˜ =
3368 (m, NH), 1550 (m, C=N), 1500 (s, N=O), 1324 (m, N–
3
over a few days at ambient temperature, yield
7
Complex 5
Method 1: [(η -C10
persed in toluene (10 mL) in a 25 mL round-bottomed flask and
the mixture was stirred. LH
added to the suspension in a portion that resulted in the formation
of [(ArNH)
less solid (92 mg, 0.269 mmol). The reaction mixture was stirred
for 5 h at room temperature and then filtered. The filtrate was evap-
orated under vacuum to afford a solid, which was subsequently
–
1 1
O) cm . H NMR (400 MHz, CDCl
3
, 298 K): δ = 1.24 [d, JH,H
], 2.29 (s, 3 H, CH ), 2.69 [m, 1 H, CH(CH
.26 (d, JH,H = 5.9 Hz, 2 H, C ), 5.46 (d, JH,H = 6.6 Hz, 2 H,
), 6.55 (s, 1 H, NH), 6.91 (d, JH,H = 9.5 Hz, 2 H, ArH), 7.23
d, JH,H = 8.7 Hz, 4 H, ArH), 7.86 (d, JH,H = 8.7 Hz, 2 H, ArH),
=
) ],
3 2
6
H
14)RuCl(μ-Cl)]
2
(100 mg, 0.163 mmol) was dis-
6
5
.6 Hz, 6 H, CH(CH
3
)
2
3
6
H
4
2-fluorophenyl
2
(228 mg, 0.668 mmol) was
6 4
C H
(
8
+
–
2-fluorophenyl
3
C] Cl (Ar = 2-FC
6
H
4
; [LH
3
]Cl) as a color-
13
1
.07 (d, JH,H = 8.7 Hz, 4 H, ArH) ppm. The C{ H} NMR spec-
trum of 7 was not recorded due to its poor solubility in CDCl
]DMSO, CD CN, and [D ]acetone. C29 27ClN Ru·CHCl
692.09 + 119.38): calcd. C 44.40, H 3.48, N 10.36; found C 44.38,
H 3.35, N 10.53.
3
,
[D
6
3
6
H
6
O
6
3
(
dissolved in CH
red crystals, yield 80% (159 mg, 0.260 mmol).
2 2
Cl and layered with n-hexane to afford 5 as dark-
General Procedure for Transfer Hydrogenation: The ruthenium(II)
complex (0.01 mmol) was dissolved in a solution of KOH
Method 2: Complex 5 was prepared from LH 2
-fluorophenyl
6
(117 mg,
2
0.343 mmol), NaOAc (28 mg, 0.341 mmol), and [(η -C10H14)-
(
1.0 mmol), ketone (1.0 mmol), and 2-propanol (4.0 mL) in a
round-bottomed flask. The solution was heated with stirring at
2 °C for 4 h and then cooled. The reaction mixture was filtered
2
RuCl(μ-Cl)] (100 mg, 0.163 mmol) in methanol (10 mL) by follow-
ing a procedure analogous to that described for complex 4 (see
Method 2), yield 81% (161 mg, 0.263 mmol), m.p. 230–232 °C. IR
8
and the volatiles from the filtrate removed under vacuum to afford
a black oil. The percentage conversion was calculated as an average
–
1 1
(
KBr): ν˜ = 3432 (m, NH), 1532 (vs, C=N), 750 (vs, C–F) cm . H
NMR (400 MHz, CDCl , 298 K): δ = 1.21 [d, JH,H = 6.6 Hz, 6 H,
CH(CH ], 2.19 (s, 3 H, CH ), 2.71 [m, 1 H, CH(CH ], 5.14,
.41 (each d, JH,H = 5.8 Hz, 2ϫ 2 H, C ), 5.96 (s, 1 H, NH),
.54 (t, JH,H = 7.3 Hz, 1 H, ArH), 6.61 (q, JH,H = 6.0 Hz, 1 H,
3
1
of two runs by H NMR spectroscopy.
3
)
2
3
3 2
)
5
6
6 4
H
CCDC-1025953 (for 1·iPr
2
O), -1025954 (for 2), -1025955 (for
O), -1025956 (for 4), -1025957 (for 5), and -1025958 (for
·CHCl ) contain the supplementary crystallographic data for this
3
7
·H
2
ArH), 6.75 (t, JH,H = 9.5 Hz, 1 H, ArH), 6.90 (m, 6 H, ArH), 7.05
3
13
1
(
(
(
m, 1 H, ArH), 7.31 (m, 2 H, ArH) ppm. C{ H} NMR
100.5 MHz, CDCl , 298 K): δ = 18.9 (CH ), 22.4 [CH(CH ], 31.2
CHMe ), 78.8, 80.4 (p-cymene ArCH), 97.3, 99.6 (p-cymene ArC),
14.5 (d, JC,F = 18.2 Hz, ArCH), 115.4 (d, JC,F = 20.1 Hz, ArCH),
22.4, 122.9 (d, JC,F = 6.7 Hz, ArCH), 123.5 (d, JC,F = 2.9 Hz,
article. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
3
3
3 2
)
2
1
1
Supporting Information (see footnote on the first page of this arti-
ArCH), 124.0 (d, JC,F = 7.7 Hz, ArCH), 124.4 (d, JC,F = 2.9 Hz, cle): Details of the synthesis and characterization of guanidines,
ArCH), 125.5 (d, JC,F = 11.5 Hz, ArCH), 126.3 (d, JC,F = 11.5 Hz, data collections, structure solution, and refinements of the crystal-
1
ArCH), 134.3 (d, JC,F = 11.5 Hz, ArC), 152.6 (d, JC,F = 243.4 Hz,
lographically characterized complexes, concentration-dependent H
ArC), 154.0 (C=N), 156.3 (d, JC,F = 244.3 Hz, ArC) ppm. 19
F
2
NMR stack plot of 3·H O, HETCOR NMR spectra of 1 and 5,
2
-chlorophenyl
4-chlorophenyl
NMR (376.5 MHz, CDCl
3
, 298 K): δ = –66.7 (NAr), –59.2 [N(H) and HRMS spectra of LH
2
and LH
2
, Car-
Ar] ppm. The 13C{ H} NMR peak assignments reported above
1
tesian coordinates of the four possible conformers of the guanidin-
were independently confirmed by 2D HETCOR NMR spec-
ate in 2, and the structural data in CIF format.
Eur. J. Inorg. Chem. 2015, 3182–3194
3193
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim