Organometallics
Article
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COMe), 159.2 (s; COMe), 158.3 (d, J(C,P) = 11.4 Hz, COMe),
158.0 (d, 3J(C,P) = 11.6 Hz, COMe), 136.7−110.1 (m; aromatic
carbon atoms), 69.3 (s; NCAr), 64.4 (s; NCH), 54.8 (s; OMe), 54.7
(s; OMe), 54.4 (s; OMe), 54.2 (s; OMe), 28.6 (s; CHMe2), 22.6 (s;
CHMe), 16.1 (s; CHMe). 31P{1H} NMR (81.0 MHz, C6D6, 20 °C): δ
(t, J(H,H) = 8.1 Hz, 2H; aromatic protons), 8.03 (d, J(H,H) = 7.1
Hz, 4H; aromatic protons), 7.89−6.31 (m, 26H; aromatic protons),
5.88 (s, 2H; aromatic protons), 4.77 (broad m, 2H; NCH), 3.44−3.24
(broad m, 4H; NH2), 2.01−1.77 (m, 26H; CMe). 13C{1H} NMR
(50.3 MHz, C6D6, 20 °C): δ 135.2−123.3 (m; aromatic carbon
atoms), 50.2 (s; NCH), 39.8 (s; CH2), 21.4 (s; CMe), 21.1 (s; CMe).
31P{1H} NMR (81.0 MHz, C6D6, 20 °C): δ −13.1 (s).
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−8.5 (d, J(P,P) = 16.0 Hz), −11.5 (d, J(P,P) = 16.0 Hz).
Synthesis of [OsCl2((R)-xylMeObiphep)((R)-daipen)] (15).
Complex 15 was prepared following the procedure used for 12, with
(R)-xylMeObiphep (88 mg, 0.127 mmol) in place of (S)-MeObiphep,
and (R)-daipen (34 mg, 0.108 mmol) instead of (R,R)-dpen. The
solution was heated at 100 °C for 45 min after the addition of the
diamine. Yield: 79 mg (63%). Anal. Calcd for C65H74Cl2N2O4OsP2: C,
61.46; H, 5.87; N, 2.21. Found: C, 61.54; H, 5.79; N, 2.29. The
product was obtained as a mixture of two diastereoisomers (ratio 4:1).
Synthesis of trans-[OsCl2((R)-xylbinap)((R)-daipen)] (20).
Complex 20 was prepared following the procedure used for 12, with
(R)-xylbinap (86 mg, 0.118 mmol) in place of (S)-MeObiphep, and
(R)-daipen (34 mg, 0.108 mmol) instead of (R,R)-dpen. Yield: 75 mg
(58%). Anal. Calcd for C71H74Cl2N2O2OsP2: C, 65.08; H, 5.69; N,
2.14. Found: C, 65.21; H, 5.83; N, 2.09. 1H NMR (200.1 MHz, C6D6,
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20 °C): δ 8.93 (t, J(H,H) = 8.3 Hz, 1H; aromatic proton), 8.74 (t,
31P{1H} NMR (81.0 MHz, C6D6, 20 °C): δ −10.4 (d, J(P,P) = 16.5
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3J(H,H) = 7.9 Hz, 1H; aromatic proton), 8.17−6.31 (m, 28H;
aromatic protons), 5.93 (d, 3J(H,H) = 12.2 Hz, 2H; aromatic protons),
4.95 (broad m, 2H; NH2 and CHN), 4.28 (broad d, J(H,H) = 8.8 Hz,
1H; NH2), 3.61 (broad m, 1H; NH2), 3.36 (s, 3H; OMe), 3.29 (m,
1H; NH2), 3.19 (s, 3H; OMe), 2.13 (s, 6H; CMe), 2.00 (s, 6H; CMe),
1.77 (s, 6H; CMe), 1.76 (s, 6H; CMe), 1.66 (m 1H; CHMe), 0.51 (d,
3J(H,H) = 6.8 Hz, 3H; CHMe), 0.02 (d, 3J(H,H) = 6.5 Hz, 3H;
CHMe). 13C{1H} NMR (50.3 MHz, C6D6, 20 °C): δ 159.2 (s;
COMe), 136.3−113.4 (m; aromatic carbon atoms), 69.3 (s; NCAr),
64.5 (s; NCH), 54.8 (s; OMe), 54.6 (s; OMe), 28.4 (s; CHMe), 22.6
(s; CHMe), 21.5 (s; CMe), 21.2 (s; CMe), 15.9 (s; CHMe). 31P{1H}
Hz), −10.8 (d, 2J(P,P) = 15.0 Hz; minor isomer), −13.2 (d, 2J(P,P) =
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15.0 Hz; minor isomer), −13.8 (d, J(P,P) = 16.5 Hz).
Synthesis of trans-[OsCl2((R)-binap)((R,R)-dpen)] (16). Com-
plex 16 was prepared following the procedure used for 12, with (R)-
binap (67 mg, 0.127 mmol) in place of (S)-MeObiphep. Yield: 63 mg
(59%). Anal. Calcd for C58H48Cl2N21OsP2: C, 63.56; H, 4.41; N, 2.56.
Found: C, 63.47; H, 4.35; N, 2.54. H NMR (200.1 MHz, C6D6, 20
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°C): δ 8.66 (t, J(H,H) = 8.4 Hz, 2H; aromatic protons), 8.23 (t,
3J(H,H) = 8.1 Hz, 6H; aromatic protons), 8.09 (t, J(H,H) = 9.4 Hz,
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6H; aromatic protons), 7.72 (d, 3J(H,H) = 8.5 Hz, 4H; aromatic
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protons), 7.40 (d, J(H,H) = 8.3 Hz, 4H; aromatic protons), 7.11−
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NMR (81.0 MHz, C6D6, 20 °C): δ −13.1 (d, J(P,P) = 16.5 Hz),
−14.6 (d, J(P,P) = 16.5 Hz).
Synthesis of trans-[OsCl2((R,S)-Josiphos*)((R,R)-dpen)] (21).
Complex 21 was prepared following the procedure used for 12, with
(R,S)-Josiphos* (76 mg, 0.107 mmol) in place of (S)-MeObiphep.
Yield: 56 mg (48%). Anal. Calcd for C56H72Cl2FeN2O2OsP2: C, 56.80;
6.34 (m, 20H; aromatic protons), 4.49 (broad m, 2H; CH), 3.85
(broad d, J(H,H) = 9.2 Hz, 2H; NH2), 3.67 (broad t, J(H,H) = 9.0 Hz,
2H; NH2). 13C{1H} NMR (50.3 MHz, C6D6, 20 °C): δ 139.4−124.8
(m, aromatic carbon atoms), 63.8 (s; NCH). 31P{1H} NMR (81.0
MHz, C6D6,, 20 °C): δ −11.2 (s).
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Synthesis of trans-[OsCl2((R)-binap)((R)-daipen)] (17). Com-
plex 17 was prepared following the procedure used for 12, with (R)-
binap (67 mg, 0.127 mmol) in place of (S)-MeObiphep, and (R)-
daipen (34 mg, 0.108 mmol) instead of (R,R)-dpen. Yield: 69 mg
(59%). Anal. Calcd for C63H58Cl2N2O2OsP2: C, 63.15; H, 4.88; N,
2.34. Found: C, 63.28; H, 4.89; N, 2.45. 1H NMR (200.1 MHz, C6D6,
20 °C): δ 8.64 (t, 3J(H,H) = 8.0 Hz, 1H; aromatic proton), 8.39−6.35
(m, 39H; aromatic protons), 4.99 (broad m, 2H; NH2 and CHN),
4.43 (broad d, J(H,H) = 10.8 Hz, 1H; NH2), 3.61 (broad t, J(H,H) =
13.8 Hz, 1H; NH2), 3.35 (s, 3H; OMe), 3.25 (m, 1H; NH2), 3.19 (s,
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H, 6.13; N, 2.37. Found: C, 56.92; H, 6.06; N, 2.29. H NMR (200.1
MHz, C6D6, 20 °C): δ 8.44−6.73 (m, 14H; aromatic protons), 5.07−
3.96 (broad m, 10H; CH, NH2, PCH, C5H3), 3.88 (s, 5H; C5H5), 3.31
(s, 3H; OMe), 3.29 (s, 3H; OMe), 2.32 (s, 6H; CMe), 2.24 (s, 6H;
CMe), 2.15−0.90 (m, 25H; CH2, Me). 13C{1H} NMR (50.3 MHz,
C6D6, 20 °C): δ 158.4 (d, 4J(C,P) = 2.2 Hz; COMe), 157.5 (d, 4J(C,P)
= 2.3 Hz; COMe), 140.4 (d, J(C,P) = 1.6 Hz; ipso Ph), 140.2 (d,
J(C,P) = 1.7 Hz; ipso Ph), 138.3 (d, 3J(C,P) = 1.7 Hz; aromatic CMe),
138.1 (d, 3J(C,P) = 2.7 Hz; aromatic CMe), 135.2−127.2 (m; aromatic
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carbon atoms), 95.8 (dd, J(C,P) = 18.7 Hz, J(C,P) = 4.2 Hz; ipso
C5H3), 72.5 (s; FeC5H3), 70.6 (s; FeC5H5), 69.2 (d, J(C,P) = 7.7 Hz;
FeC5H3), 67.0 (d, J(C,P) = 6.0 Hz; FeC5H3), 64.0 (s; NCH), 63.3 (s;
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3H; OMe), 1.74 (m 1H; CHMe), 0.52 (d, J(H,H) = 6.8 Hz, 3H;
CHMe), 0.02 (d, 3J(H,H) = 7.5 Hz, 3H; CHMe). 13C{1H} NMR (50.3
MHz, C6D6, 20 °C): δ 159.3 (s; COMe), 159.2 (s; COMe), 136.3−
113.6 (m; aromatic carbon atoms), 69.3 (s; NCAr), 64.7 (s; NCH),
54.9 (s; OMe), 54.7 (s; OMe), 28.6 (s; CHMe), 22.6 (s; CHMe), 16.1
(s; CHMe). 31P{1H} NMR (81.0 MHz, C6D6, 20 °C): δ −9.81 (d,
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NCH), 59.2 (s; OMe), 59.1 (s; OMe), 42.4 (d, J(C,P) = 25.2 Hz;
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PCH of Cy), 39.5 (d, J(C,P) = 19.5 Hz; PCH of Cy), 31.8 (d;
1J(C,P) = 22.1 Hz; PCMe), 31.7−27.2 (m; CH2 of Cy), 21.3 (s; Me),
16.6 (d, J(C,P) = 8.5 Hz; PCMe). 31P{1H} NMR (81.0 MHz, C6D6,
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2J(P,P) = 16.5 Hz), −11.8 (d, J(P,P) = 16.5 Hz).
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20 °C): δ 2.0 (d, J(P,P) = 22.0 Hz), −11.6 (d, J(P,P) = 22.0 Hz).
Synthesis of trans-[OsHCl(P(m-tolyl)3)2(en)] (22). Complex 1b
(100 mg, 0.049 mmol) was dissolved in toluene (20 mL), and NEt3
(20 μL, 0.143 mmol) was added under H2 (1 atm). The solution was
heated at 120 °C for 4 h. En (4.9 μL, 0.073 mmol) was added at room
temperature, and the solution was heated at 60 °C for 3 h under H2.
The resulting solution was concentrated (0.5 mL), and addition of
diethyl ether (4 mL) afforded the precipitation of NEt4Cl, which was
fine-filtered and washed with diethyl ether (2 × 3 mL) and toluene (1
× 2 mL). The filtrate was concentrated (1 mL), and addition of
heptane (4 mL) resulted in the precipitation of a yellow product,
which was filtered off, washed with heptane (3 × 5 mL) at 60 °C, and
dried under reduced pressure. Yield: 50 mg (57%). Anal. Calcd for
C44H51ClN2OsP2: C, 59.02; H, 5.74; N, 3.13. Found: C, 59.23; H,
Synthesis of trans-[OsCl2((S)-xylbinap)((R,R)-dpen)] (18).
Complex 18 was prepared following the procedure used for 12, with
(S)-xylbinap (79 mg, 0.108 mmol) in place of (S)-MeObiphep. After
the usual workup, the product was purified through silica gel (toluene)
to remove traces of tri-m-tolylphosphine. Yield: 60 mg (51%). Anal.
Calcd for C66H64Cl2N2OsP2: C, 65.61; H, 5.34; N, 2.32. Found: C,
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65.52; H, 5.22; N, 2.43. H NMR (200.1 MHz, C6D6, 20 °C): δ 8.90
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(t, J(H,H) = 8.0 Hz, 2H; aromatic protons), 8.20 (d, J(H,H) = 8.4
Hz, 4H; aromatic protons), 7.83−6.48 (m, 26H; aromatic protons),
5.91 (s, 2H; aromatic protons), 4.66 (broad m, 2H; NCH), 4.58
(broad m, 2H; NH2), 3.49 (broad m, 2H; NH2), 2.04 (s, 12H; CMe),
1.81 (s, 12H; CMe). 13C{1H} NMR (50.3 MHz, C6D6, 20 °C): δ
135.2−123.3 (m; aromatic carbon atoms), 63.8 (s; NCH), 21.5 (s;
CMe), 21.3 (s; CMe). 31P{1H} NMR (81.0 MHz, C6D6, 20 °C): δ
−13.3 (s).
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5.88; N, 3.21. H NMR (200.1 MHz, C6D6, 20 °C): δ 7.93−6.72 (m,
24H; Ph), 2.79 (broad s, 2H; CH2), 2.58 (broad s, 2H; CH2), 2.06−
1.90 (m, 20H; CH3, NH2), 1.56 (broad s, 2H; NH2), - 20.9 (t, 2J(P,H)
= 16.3 Hz, 1H; OsH). 13C{1H} NMR (50.3 MHz, C6D6, 20 °C): δ
138.3−125.8 (m; aromatic carbon atoms), 45.5 (s; NCH2), 21.5 (s;
CH3). 31P{1H} NMR (81.0 MHz, C6D6, 20 °C): δ 20.1 (s).
Synthesis of trans-[OsCl2((S)-xylbinap)((R,R)-dppn)] (19).
Complex 19 was prepared following the procedure used for 18, with
(R,R)-dppn (24 mg, 0.106 mmol) in place of (R,R)-dpen. Alter the
usual workup, the product was purified through silica gel (toluene) to
remove traces of tri-m-tolylphosphine. Yield: 59 mg (49%). Anal.
Calcd for C67H66Cl2N2OsP2: C, 65.84; H, 5.44; N, 2.29. Found: C,
Synthesis of trans-[OsHCl(dppf)(en)] (23). Complex 1a (100
mg, 0.095 mmol) was dissolved in toluene (20 mL), and NEt3 (20 μL,
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65.74; H, 5.57; N, 2.37. H NMR (200.1 MHz, C6D6, 20 °C): δ 9.01
J
Organometallics XXXX, XXX, XXX−XXX