J. Bravo et al.
ARTICLE
(br. s, PC). 13C{1H} NMR (100 MHz, CD2Cl2): δ = 51.3 (s, OCH3), (See Scheme 2 for labelling): δ = 198.1 (br., PC), 202.0 (br., PB), 213.2
65.8 (s, OCH2CH2O), 127.2–148.0 (Ph), 225.6 (br. m, CO).
(br., PA). 13C{1H} NMR (100 MHz, CD2Cl2):
δ
=
15.0–20.0
2
[CH(CH3)2], 30.1–38.1 [CH(CH3)2], 51.5 (d, JC,P = 3.4 Hz, OCH3),
65.6 (s, OCH2CH2O), 67.0 (s, OCH2CH2O), 227.0 (br., CO).
Compound 1b: Yield ≥47 %. Anal. C34H40MnO7P3 (708.55); C 57.27
(calcd. 57.64); H 5.70 (calcd. 5.69)%. MS (referred to the most abunꢀ
dant isotopes): m/z = 708 [M+], 486 [M+ – P(OEt)3 – 2CO]. IR (KBr):
Compound 2b: Yield ≥50 %. Anal. C22H48MnO7P3 (572.48) C 45.89
(calcd. 46.16); H 8.03 (calcd. 8.45)%. MS (referred to the most abunꢀ
ν = 1931 (s), 1869 (s) cm–1. H NMR (400 MHz, CD Cl ): δ = –7.27
1
˜
2
2
2
3
dant isotopes): m/z = 572, [M+], 486 [M+ – P(OEt)3 – 2CO]. IR (KBr):
(dt, JP,H = 58.5, 49.9 Hz, 1 H, MnH), 0.96 (t, JH,H = 6.80 Hz, 9 H,
OCH2CH3), 3.62 (m, 6 H, OCH2CH3), 4.10 (m, 4 H, OCH2CH2O),
7.00–8.00 (m, 20 H, Ph). 31P{1H} NMR (161 MHz, CD2Cl2) (See
Scheme 2 for labelling): δ = 180.9 (m, PA, PB), 189.8 (m, PC). 13C{1H}
ν = 1921 (s), 1860 (s) cm–1. H NMR (400 MHz, CD Cl ): δ = –7.53
1
˜
2
2
(br., 1 H, MnH), 1.20 [br, 24 H, CH(CH3)2; 9 H, OCH2CH3], 2.20 [br,
4 H, CH(CH3)2], 4.00 (br, 4 H, OCH2CH2O; 6 H, OCH2CH3). 31P{1H}
NMR (161 MHz, CD2Cl2) (See Scheme 2 for labelling): δ = 192.0
(br., PC), 203.0 (br., PA), 213.0 (br., PB). 13C{1H} NMR (100 MHz,
15.2–20.0 [CH(CH3)2; OCH2CH3], 30.1–37.0
[CH(CH3)2], 60.2 (br. s, OCH2CH3), 65.6 (s, OCH2CH2O), 66.9
(s,OCH2CH2O), 227.1 (m, CO).
NMR (100 MHz, CD2Cl2):
OCH2CH3), 65.7 (s, OCH2CH2O), 127.0–146.6 (Ph), 225.7 (m, CO).
δ = 16.1 (s, OCH2CH3), 60.2 (s,
CD2Cl2):
δ
=
Compound 1c: Yield ≥48 %. Anal. C36H36MnO6P3 (712.54); C 60.55
(calcd. 60.68); H 5.19 (calcd. 5.09)%. MS (referred to the most abunꢀ
dant isotopes): m/z = 712 [M+], 486 [M+ – PPh(OMe)2 – 2CO]. IR
(KBr): ν = 1932 (s), 1874 (s), 1831 (m) cm–1. H NMR (400 MHz,
1
˜
Compound 2c: Yield ≥44 %. Anal. C24H44MnO6P3 (576.47); C 49.74
(calcd. 50.01); H 8.02 (calcd. 7.69)%. MS (referred to the most abunꢀ
dant isotopes): m/z = 576 [M+], 486 [M+ – PPh(OMe)2 – 2CO]. IR
2
CD2Cl2): δ = –6.94 (dt, JP,H = 50.8, 56.2 Hz, 1 H, MnH), 3.04 (d,
3JH,P = 10.9 Hz, 3 H, OCH3), 3.07 (d, JH,P = 11.0 Hz, 3 H, OCH3),
3
3.50–4.40 (m, 4 H, OCH2CH2O), 7.10–7.93 (m, 25 H, Ph). 31P{1H}
NMR (161 MHz, CD2Cl2) (See Scheme 2 for labelling): δ = 179.9 (m,
PA, PB), 208.6 (m, PC). 13C{1H} NMR (100 MHz, CD2Cl2): δ = 51.4
(s, OCH3), 65.4 (s, OCH2CH2O), 126.9–132.3 (Ph), 141.3–146.2 (Ph),
225.2 (m, CO).
(KBr): ν = 1918 (s), 1857 (s) cm–1. 1H NMR (400 MHz, CD2Cl2):
˜
δ = –7.31 (br., 1 H, MnH), 0.98–1.70 [m, 24 H, CH(CH3)2], 2.01–2.60
3
[m, 4 H, CH(CH3)2], 3.61 (d, JH,P = 10.9 Hz, 9 H, OCH3), 3.82–4.51
(m, 4 H, OCH2CH2O), 6.8–8.0 (m, 5 H, Ph). 31P{1H} NMR (161 MHz,
CD2Cl2) (See Scheme 2 for labelling): δ = 203.5 (br., PA, PB), 210.8
(br., PC). 13C{1H} NMR (100 MHz, CD2Cl2):
δ = 14.8–19.8
Compound 1d: Yield ≥45 %. Anal. C38H40MnO6P3 (740.59); C 61.58
(calcd. 61.63); H 5.38 (calcd. 5.44)%. MS (referred to the most abunꢀ
[CH(CH3)2], 30.4–36.9 [CH(CH3)2], 52.0 (br. s, OCH3), 65.3 (s,
OCH2CH2O), 67.2 (s, OCH2CH2O), 226.3 (m, CO).
dant isotopes): m/z = 740 [M+], 486 [M+ – PPh(OEt)2 – 2CO]. IR
(KBr): ν = 1932 (s), 1872 (s), 1830 (m) cm–1. H NMR (400 MHz,
1
˜
Compound 2d: Yield ≥40 %. Anal. C26H48MnO6P3 (604.52); C 51.58
(calcd. 51.66); H 7.77 (calcd. 8.00)%. MS (referred to the most abunꢀ
dant isotopes): m/z = 604 [M+], 486 [M+ – PPh(OEt)2 – 2CO]. IR
2
CD2Cl2): δ = –6.90 (dt, JP,H = 53.0, 54.4 Hz, 1 H, MnH), 0.89–0.93
(m, 6 H, OCH2CH3), 3.00–4.35 (m, 4 H, OCH2CH3; 4 H, OCH2CH2O
), 7.16–7.80 (m, 25 H, Ph). 31P{1H} NMR (161 MHz, CD2Cl2) (See
Scheme 2 for labelling): δ = 179.6–181.1 (m, PA, PB), 202.4 (m, PC).
13C{1H} NMR (100 MHz, CD2Cl2): δ = 16.0 (s, OCH2CH3), 16.1 (s,
(KBr): ν = 1917 (s), 1859 (s) cm–1. 1H NMR (400 MHz, CD2Cl2):
˜
δ = –7.21 (br., 1 H, MnH), 0.87–1.39 [m, 24 H, CH(CH3)2; 6 H,
OCH2CH3], 2.03–2.62 [m, 4 H, CH(CH3)2], 3.37–4.60 [m, 4 H,
OCH2CH2O; 4 H, OCH2CH3], 7.18–7.69 (m, 5 H, Ph). 31P{1H} NMR
(161 MHz, CD2Cl2) (See Scheme 2 for labelling): δ = 204.9 (m, PA,
PB), 210.7 (m, PC). 13C{1H} NMR (100 MHz, CD2Cl2): δ = 16.1–20.0
[CH(CH3)2; OCH2CH3], 30.1–36.0 [CH(CH3)2], 61.4 (br., OCH2CH3),
62.9 (br., OCH2CH3), 65.7 (br., OCH2CH2O), 127.6–132.6 (Ph), 227.2
(m, CO).
2
2
OCH2CH3), 61.2 (d, JC,P = 4.1 Hz, OCH2CH3), 61.4 (d, JC,P
8.3 Hz, OCH2CH3), 65.7 (s, OCH2CH2O), 127.2–133.0 (Ph), 141.7–
143.2 (Ph), 225.5 (m, CO).
=
Preparation of cis,merꢀ[MnH(CO)2(L2)(L')]; [L' = P(OMe)3
(2a), P(OEt)3 (2b), PPh(OMe)2 (2c), PPh(OEt)2 (2d)]
To a solution of [MnH(CO)3(L2)] (0.15 g, 0.35 mmol) in toluene
(15 mL) was added an excess of the appropriate phosphite or phosꢀ
XꢀRay Crystallographic Analysis
phonite ligand in a 1:3 molar ratio. The reaction mixture was irradiated Compounds 2 and 3 were mounted on glass fibers and studied on a
with UV light at room temperature for about 10 h. The solvent was Bruker Smart 1000 CCD diffractometer using graphite monochroꢀ
evaporated under reduced pressure and the resulting oil was purified mated MoꢀKα radiation (λ = 0.71073 Å) with corrections for Lorentz
by chromatography on a silica gel column (length 46 cm, diameter and polarization effects. The software SMART [16] was used for colꢀ
1.5 cm) using a mixture of light petroleum (40–60 °C) and diethyl lecting frames of data, indexing reflections, and the determination of
ether in a 10:5 (v/v) ratio as eluent. The first fraction eluted (35 mL) lattice parameters. SAINT [17] was used to integrate the intensity of
was evaporated to dryness. The resulting oil was treated with ethanol reflections and scaling, and SADABS [18] was used for empirical abꢀ
or methanol (3–5 mL) depending on the OR group. A yellow solid sorption correction.
slowly separated from the resulting solution and this was filtered off,
dried under vacuum, and recrystallized from a 2:10 (v/v) CH2Cl2/
MeOH (EtOH) solution by slow evaporation of the solvent.
Both structures were solved and refined with the Oscail program [19]
by direct methods and refined by fullꢀmatrix leastꢀsquares based on F2
[20]. Nonꢀhydrogen atoms were refined with anisotropic displacement
Compound 2a: Yield ≥56 %. Anal. C19H42MnO7P3 (530.40); C 42.89 parameters. Hydrogen atoms were included in idealized positions and
(calcd. 43.03); H 7.56 (calcd. 7.98)%. MS (referred to the most abunꢀ refined with isotropic displacement parameters – except for those
dant isotopes): m/z = 530 [M+], 350 [M+ – P(OMe)3 – 2CO]. IR (KBr): bonded to the metal atom, which were located in the density map and
1
ν = 1925 (s), 1863 (s) cm–1. H NMR (400 MHz, CD Cl ): δ = –7.31 refined isotropically. Details of crystal data and structural refinement
˜
2
2
(dt, 2JP,H = 59.0, 49.0 Hz, 1 H, MnH), 0.98–1.70 [m, 24 H, CH(CH3)2], are given in Table 4. ORTEP [21] drawings of the compounds, along
3
2.01–2.60 [m, 4 H, CH(CH3)2], 3.61 (d, JH,P = 10.9 Hz, 9 H, OCH3), with the numbering schemes adopted, are shown in Figure 1 and Figꢀ
3.82–4.51 (m, 4 H, OCH2CH2O). 31P{1H} NMR (161 MHz, CD2Cl2) ure 2.
2508
© 2009 WILEYVCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2009, 2503–2510