10.1002/ejic.201900987
European Journal of Inorganic Chemistry
FULL PAPER
138.49, 130.83, 128.10, 126.78, 120.77. HR-ESI (m/z): calculated
466.0455 (C21H12MnN7O3, [M+H]+) found 466.0433. Crystals suitable for
X-ray analysis were grown via vapour diffusion of petroleum spirits (40-
60 °C) into a solution of dichloromethane containing the complex.
2031 (s) (CO), 1934 (s) (2 x CO). 1H NMR (δ, ppm, Acetone-d6): 8.48 (2H,
'
’
’
d, J = 3.6 Hz, H8 ), 8.00 (2H, s, H1 ), 7.89 (2H, s, H5 ), 7.65 - 7.59 (12H, m,
’
H2,3,4,6’), 3.55 (6H, s, H6 ). 13C NMR (δ, ppm, DMSO-d6): 164.19, 160.88,
150.21, 149.44, 147.81, 136.50, 135.47, 129.63, 129.53, 129.03, 127.23,
125.38, 123.77, 119.69, 29.12. HR-ESI (m/z): calculated 646.1394
(C35H24MnN7O3, [M+H]+) found 646.1379.
fac-Mn(phen)(CO)34
fac-Mn(batho)(CO)34
Yield 40 mg (63 %). Elemental analysis for C23H12MnN7O3: calculated C
56.45, H 2.47, N 20.04; found C 56.63, H 2.32, N 20.05. νmax (ATR)/cm−1
:
2036 (s) (CO), 1942 (s) (2 x CO). 1H NMR (δ, ppm, Acetone-d6): 9.74 (2H,
Yield 41 mg (68%). Elemental analysis for C37H24MnN7O3: calculated C
dd, 3JH-H = 5.2 Hz, 4JH-H = 0.8 Hz, H4), 8.86 (2H, dd, 3JH-H = 8.4 Hz, 4JH-H
=
66.37, H 3.61, N 14.64; found C 66.36, H 3.52, N 14.42. νmax (ATR)/cm−1
:
0.8 Hz H2), 8.24 (2H, s, H1), 8.14 (2H, dd, 3JH-H = 8.0 Hz, JH-H = 1.2 Hz,
2031 (s) (CO), 1934 (s) (2 x CO). 1H NMR (δ, ppm, Acetone-d6): 8.00 (2H,
3
3
3
/
H3), 7.84 (2H, d, JH-H = 8.4 Hz, H6) 7.65 (2H, d, JH-H = 8.4 Hz, H5). 13C
NMR (δ, ppm, Acetone-d6): 162.82, 155.31, 147.96, 139.19, 135.80,
133.16, 130.83, 128.11, 127.03, 126.80, 119.37, 111.96. HR-ESI (m/z):
calculated 490.0455 (C23H12MnN7O3, [M+H]+) found 490.0437. Crystals
suitable for X-ray analysis were grown via vapour diffusion of petroleum
spirits (40-60 °C) into a solution of dichloromethane containing the
complex.
s, H1 ), 7.90-7.88 (4H, m, H5,7), 7.68 (2H, dd, 1H, dd, 3JH-H = 5.6 Hz, 4JH-H
’
’
= 1.6 Hz, H8 ), 7.64-7.60 (10H, m, H2,3,4’), 3.55 (6H, s, H6 ). 13C NMR (δ,
ppm, DMSO-d6): 164.19, 161.47, 149.44, 147.80, 135.46, 133.80, 132.80,
129.63, 129.53, 129.04, 127.23, 125.95, 125.38, 123.77, 118.7, 110.67,
29.13. HR-ESI (m/z): calculated 670.1394 (C37H24MnN7O3, [M+H]+) found
670.1386.
fac-Mn(batho)(CO)35
fac-Mn(phen)(CO)35
Yield 45 mg (73%). Elemental analysis for C37H25MnN6O4: calculated C
Yield 46 mg (39%). Elemental analysis for C23H13MnN6O4: calculated C
66.07, H 3.75, N 12.49; found C 66.32, H 3.81, N 12.41. νmax (ATR)/cm−1
:
56.11, H 2.66, N 17.07; found C 55.77, H 2.47, N 16.92. νmax (ATR)/cm−1
:
2031 (s) (CO), 1934 (s) (2 x CO). 1H NMR (δ, ppm, Acetone-d6): 9.98 (1H,
2036 (s) (CO), 1942 (s) (2 x CO). 1H NMR (δ, ppm, Acetone-d6): 9.96 (1H,
s, H7) 9.75 (2H, dd, 3JH-H = 4.8 Hz, 4JH-H = 1.2 Hz, H4), 8.86 (2H, dd, 3JH-H
= 8.4 Hz, 4JH-H = 1.2 Hz, H2), 8.24 (2H, s, H1), 8.15 (2H, dd, 3JH-H = 8.4 Hz,
3JH-H = 5.2 Hz, H3), 7.89-7.87 (2H, m, H6’), 7.81-7.79 (2H, m, H5). 13C NMR
(δ, ppm, Acetone-d6): 192.36, 163.26, 155.30, 148.00, 139.16, 137.11,
136.96, 130.84, 130.51, 128.10, 126.89, 126.78. HR-ESI (m/z): calculated
493.0452 (C23H13MnN6O4, [M+H]+) found 493.0429. Crystals suitable for
X-ray analysis were grown via vapour diffusion of ether into a solution of
dichloromethane containing the complex.
s, H9’), 8.00 (2H, s, H1’), 7.92 (2H, d, 3JH-H = 8.4 Hz, H8’), 7.89 (2H, s, H5 ),
’
’
7.83 (2H, d, 3JH-H = 8.4 Hz, H7 ), 7.65 - 7.61 (10H, m, H2,3,4’), 3.56 (6H, s,
’
H6 ). 13C NMR (δ, ppm, DMSO-d6): 192.63, 164.24, 161.90, 149.49, 147.91,
135.82, 135.52, 134.99, 130.10, 129.68, 129.59, 129.09, 127.24, 125.91,
125.43, 123.80, 29.17. HR-ESI (m/z): calculated 673.1391 (C37H25MnN6O4,
[M+H]+) found 673.1381.
X-ray diffraction analysis
All crystals were grown via the diffusion of petroleum spirits into
dichloromethane. Crystallographic data for the structures were collected
fac-Mn(batho)(CO)31
at 100(2)
K on either an Oxford Diffraction Xcalibur or Gemini
Yield 52 mg (79%). Elemental analysis for C36H25MnN6O3: calculated C
diffractometer. Following Lp, and absorption corrections, and solution by
direct methods, the structures were refined against F2 with full-matrix least
squares using the program SHELXL-2014.9.[49] Anisotropic displacement,
parameters were employed for the non-hydrogen atoms. All hydrogen
atoms were added at calculated positions and refined by use of a riding
model with isotropic displacement parameters based on those of the
parent atom. Crystallographic data for the structures reported in this paper
can be found in the Supporting Information and have been deposited at
the Cambridge Crystallographic Data Centre. CCDC numbers are given
below. Copies of the data can be obtained free of charge via
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
67.08, H 3.91, N 13.04; found C 66.80, H 3.70, N 13.04. νmax (ATR)/cm−1
:
2030 (s) (CO), 1932 (s) (2 x CO). 1H NMR (δ, ppm, Acetone-d6): 7.99 (2H,
s, H1’), 7.88 (2H, s, H5’), 7.74 - 7.71 (2H, m, H7’), 7.65 - 7.60 (10H, m,
H2,3,4’ ), 7.28 – 7.21 (3H, m, H8,9’) 3.55 (6H, s, H6’). 13C NMR (δ, ppm,
DMSO-d6): 164.09, 162.54, 149.35, 147.85, 135.49, 129.70, 129.61,
129.48, 129.00, 128.53, 128.29, 127.14, 125.41, 125.35, 123.72, 29.08.
HR-ESI (m/z): calculated 645.1441 (C36H25MnN6O3, [M+H]+) found
645.1428.
fac-Mn(batho)(CO)32
Yield 35 mg (63%). Elemental analysis for C35H24MnN7O30.2CH2Cl2:
calculated C 63.81, H 3.71, N 14.80; found C 64.03, H 3.50, N 14.79. νmax
(ATR)/cm−1: 2031 (s) (CO), 1934 (s) (2 x CO). (δ, ppm, Acetone-d6): 8.88
Mn(phen)(CO)31, C22H13MnN6O3, M = 464.32 , 0.168 x 0.145 x 0.102 mm3,
triclinic, space group P1,¯, a = 9.2137(4), b = 9.3093(5), c = 12.8795(7) Å,
α = 106.306(4), β = 96.016(4), γ = 109.134(4)°, V = 977.82(9) Å3, Z = 2, Dc
= 1.577 g/cm3, μ = 0.715 mm-1. λ = 0.71073 Å, T = 100(2) K, 2max = 65.2º,
12385 reflections collected, 6444 unique (Rint = 0.0337). Final GooF =
1.000, R1 = 0.0431, wR2 = 0.0918, R indices based on 5129 reflections
with I > 2(I), ||max= 0.50(8) e Å-3, 289 parameters, 0 restraints. CCDC
number 1938962.
’
(1H, d, 4JH-H = 1.2 Hz, H7’), 8.43 (1H, dd, 3JH-H = 4.8 Hz, 4JH-H = 1.6 Hz, H9 )
’
8.01-7.98 (3H, m, H1,11’), 7.89 (2H, s, H5 ), 7.65 - 7.59 (10H, m, H2,3,4’), 7.27
’
(1H, dd, 3JH-H = 8.4 Hz, 3JH-H = 4.8 Hz, H10’), 3.56 (6H, s, H6 ). 13C NMR (δ,
ppm, DMSO-d6): 164.15, 160.35, 149.38, 147.82, 147.63, 146.45, 135.47,
132.63, 129.60, 129.49, 128.99, 128.69, 127.20, 125.47, 125.36, 123.73,
29.11. HR-ESI (m/z): calculated 646.1407 (C23H13MnN6O4, [M+H]+) found
646.1381.
Mn(phen)(CO)32, C21H12MnN7O3, M = 465.32, 0.224 x 0.188 x 0.143 mm3,
triclinic, space group P1,¯, a = 9.1185(3), b = 9.2141(3), c = 12.7940(4) Å,
α = 95.906(3), β = 104.413(3), γ = 108.911(3)°, V = 964.94(6) Å3, Z = 2, Dc
= 1.601 g/cm3, μ = 0.726 mm-1. λ = 0.71073 Å, T = 100(2) K, 2max = 64.6°,
fac-Mn(batho)(CO)33
Yield 37 mg (64%). Elemental analysis for C35H24MnN7O3: calculated C
65.11, H 3.75, N 15.19; found C 65.17, H 3.56, N 14.95. νmax (ATR)/cm−1
:
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