Organometallics
Article
1H NMR (298 K, C6D6): δ 7.58 (s, 4H, Ph), 7.28 (m, 1H, HAr), 7.00
(m, 7H, Ph and HAr), 6.67 (m, 1H, HAr), 6.45 (m, 1H, HAr), 4.85 (br,
2H, CH nbd), 3.50 (br, 2H, CH nbd), 3.25 (br, 2H, CH nbd),
2.89 (s, 3H, CH3), 1.29 (m, 2H, CH2 nbd). 31P{1H} NMR (298 K,
C6D6): δ 38.4 (d, JP‑Rh = 183.1). 13C{1H} NMR (298 K, C6D6): δ
170.0 (dd, JC‑P = 28.3, JC‑Rh = 3.5, Ci‑N‑Ar), 133.8 (CAr), 133.8 (CAr),
133.0 (d, JC‑P = 12.3, Co, Ph), 132.6 (dd, JC‑P = 44.2, JC‑Rh = 1.9, Ci,
Ph), 129.9 (d, JC‑P = 2.2, Cp, Ph), 128.7 (d, JC‑P = 10.0, Cm, Ph), 117.2
(dd, JC‑P = 48.3, JC‑Rh = 1.1, Ci‑P‑Ar), 113.4 (d, JC‑P = 7.1, CAr), 109.9
(dd, JC‑P = 14.0, JC‑Rh =1.7, CAr), 86.6 (d, JC‑Rh = 6.0, =CH nbd), 86.5
(d, JC‑Rh = 5.7, CH nbd), 64.4 (dd, JC‑Rh = 4.4, JC‑P = 1.9, CH2
nbd), 52.2 (CH nbd), 49.8 (d, JC‑Rh = 9.8, CH nbd), 39.1 (CH3).
Synthesis of [Rh2(diene){μ-NH(CH2)3PPh2}2]. General Method.
In a dry box, potassium bis(trimethylsilyl)amide (KHDMS) was
added to a solution of Ph2P(CH2)3NH2 in THF (2 mL). The solution
was transferred to a suspension of the corresponding dinuclear
compound [Rh(μ-Cl)(diene)]2 in THF (8 mL) to give red solutions,
which were stirred for 1 h at room temperature. The solutions were
filtered to eliminate the KCl formed and then brought to dryness
under vacuum to give red-orange solids, which were washed with n-
hexane (3 × 2 mL) and dried under vacuum. Recrystallization from
THF/n-hexane was necessary to obtain pure compounds.
F tfb), 138.4 (d, JC‑P = 18.8, Ci), 138.2 (d, JC‑P = 19.5, Ci), 138.6 (d,
JC‑F = 255.5, C-F tfb), 134.1 (m, Co), 128.5 (Cp), 127.41 (m, Cm),
51.2 (d, JC‑Rh = 10.6, CH tfb), 50.9 (d, JC‑Rh = 10.0, CH tfb),
50.1 (CH2N), 40.8 (CH tfb), 40.6 (CH tfb), 29.6 (d, JC‑P = 24.2,
CH2P), 29.4 (CH2).
Synthesis of [Rh(diene){Ph2P(CH2)3NHR}][BF4] (R = Me, H).
General Method. AgBF4 was added to a suspension of the
corresponding dinuclear compound [Rh(μ-Cl)(diene)]2 in THF
(10 mL) and the reaction mixture stirred for 30 min in the dark. The
suspension was filtered and washed with THF (3 × 1 mL). The
resulting solution was concentrated under vacuum to ca. 5 mL and
then added slowly to a solution of the functionalized phosphine,
Ph2P(CH2)3NHMe or Ph2P(CH2)3NH2, in THF (5 mL) at 273 K
giving immediately yellow suspensions of the compounds. The solvent
was removed under vacuum, and the yellow residue washed with
diethyl ether (3 × 2 mL) and dried under vacuum.
[Rh(cod){Ph2P(CH2)3NHMe}][BF4] (6). [Rh(μ-Cl)(cod)]2 (100
mg, 0.203 mmol), AgBF4 (79.0 mg, 0.406 mmol), Ph2P(CH2)3NHMe
(104 mg, 0.406 mmol). Yield: 72%. Anal. Calcd. for C24H32BF4NPRh:
C, 51.92; H, 5.81; N, 2.52. Found: C, 51.64; H, 5.74; N, 2.48. MS
(MALDI-Tof, CH2Cl2, m/z, %): 468.1 ([M]+, 100). ΛM (acetone, 5.0
1
× 10−4 M) = 42 Ω−1 cm2 mol−1. H NMR (298 K, CD2Cl2): δ 8.01
(m, 2H, Ph), 7.65 (m, 3H, Ph), 7.37 (m, 3H, Ph), 7.09 (m, 2H, Ph),
5.39 (br, 1H, CH cod), 5.05 (br, 1H, CH cod), 4.10 (br, 1H,
NH), 3.73 (br, 1H, CH cod), 3.16 (m, 1H, CH2), 3.03−2.88 (m,
2H; 1H CH cod, 1H, CH2), 2.68−1.97 (m, 8H; 6H, CH2 cod, 2H,
CH2), 2.23 (d, JH‑H = 6.1, 3H, CH3), 2.12−1.86 (m, 3H; 1H, CH2,
2H, CH2 cod), 1.68 (m, 1H, CH2). 31P{1H} NMR (298 K, CD2Cl2):
δ 17.0 (d, JP‑Rh = 155.2). 13C{1H} NMR (298 K, CD2Cl2): δ 135.6 (d,
JC‑P = 12.6, Co), 133.0 (d, JC‑P = 2.2, Cp), 131.5 (d, JC‑P = 9.0, Co),
[Rh2(cod){μ-NH(CH2)3PPh2}2] (3). [Rh(μ-Cl)(cod)]2 (100 mg,
0.203 mmol), Ph2P(CH2)3NH2 (98.8 mg, 0.406 mmol), KHDMS (82
mg, 0.411 mmol). Yield: 76%. Anal. Calcd. for C38H46N2P2Rh2: C,
57.16; H, 5.81; N, 3.51. Found: C, 57.32; H, 5.82; N, 3.50. MS (ESI+,
THF, m/z, %): 589.1 ([Rh(Ph2P(CH2)3NH2)2]+, 100), 454.2
+
1
([Rh(cod)(Ph2P(CH2)3- NH2)] , 20). H NMR (298 K, C6D6): δ
7.93 (m, 4H, Ph), 7.46 (m, 4H, Ph), 7.07−6.88 (m, 12H, Ph), 3.88
(br, 2H, CH cod), 3.66 (br, 2H, CH cod), 2.82 (m, 4H, CH2N +
CH2), 2.60 (m, 2H, CH2P), 2.27 (m, 2H, CH2N), 2.09 (m, 4H,
CH2P + CH2), 1.91 (m, 2H, CH2 cod), 1.79 (m, 2H, CH2 cod), 1.54
(m, 2H, CH2 cod), 1.37 (m, 2H, CH2 cod), −0.17 (m, 2H, NH).
31P{1H} NMR (298 K, C6D6): δ 38.0 (d, JP‑Rh = 172.0). 13C{1H}
NMR (298 K, C6D6): δ 138.8 (d, JC‑P = 8.3, Ci), 138.4 (d, JC‑P = 9.0,
Ci), 134.0 (m, Co), 133.7 (m, Co), 130.9 (m, Cm), 128.4 (m,
Cm),127.0 (Cp), 126.9 (Cp), 75.6 (d, JC‑Rh = 12.4, CH cod), 75.4
(d, JC‑Rh = 12.6, CH cod), 47.3 (CH2N), 32.1 (CH2P), 31.4 (CH2),
131.0 (d, JC‑P = 9.3, Ci), 130.9 (d, JC‑P = 2.3, Cp ), 130.2 (d, J
=
C‑P
10.2, Cm), 129.9 (d, JC‑P = 12.7, Ci), 129.3 (d, JC‑P = 9.6, Cm), 108.5
(dd, JC‑Rh = 9.7, JC‑P = 6.8, CH cod), 105.0 (dd, JC‑Rh = 10.8, JC‑P
=
=
6.8, CH cod), 79.1 (d, JC‑Rh = 12.1, CH cod), 76.1 (d, JC‑Rh
11.6, CH cod), 53.3 (d, JC‑P = 3.1, CH2N), 39.5 (CH3), 33.8, 31.0,
30.7, 28.3 (CH2 cod), 24.0 (d, JC‑P = 25.2, CH2P), 19.2 (CH2).
[Rh(nbd){Ph2P(CH2)3NHMe}][BF4] (7). [Rh(μ-Cl)(nbd)]2 (100
mg, 0.217 mmol), AgBF4 (84.5 mg, 0.434 mmol), Ph2P(CH2)3NHMe
(112 mg, 0.434 mmol). Yield: 58%. Anal. Calcd. for C23H28BF4NPRh:
C, 51.24; H, 5.24; N, 2.60. Found: C, 51.20; H, 5.21; N, 2.59. MS
(MALDI-Tof, CH2Cl2, m/z, %): 452.1 ([M]+, 100). ΛM (acetone, 5.0
× 10−4 M ) = 46 Ω−1 cm2 mol−1. 1H NMR (298 K, CD2Cl2): δ 7.77
(m, 2H, Ph), 7.57 (m, 3H, Ph), 7.44 (m, 3H, Ph), 7.24 (m, 2H, Ph),
5.65 (br, 1H, CH nbd), 5.53 (br, 1H, CH nbd), 3.95 (br, 1H,
CH nbd), 3.87 (m, 2H, CH nbd y NH), 3.56 (br, 1H, CH nbd),
3.24 (br, 1H, CH nbd), 3.06 (t, JH‑H = 11.9, 1H, CH2N), 2.82 (m,
1H, CH2N), 2.44 (m, 1H, CH2P), 2.35 (m, 1H, CH2P), 2.29 (d, JH‑H
= 6.1, 3H, CH3), 1.82 (m, 1H, CH2), 1.65 (m, 1H, CH2), 1.48 (d,
JH‑H = 11.5, 2H, CH2 nbd).31P{1H} NMR (298 K, CD2Cl2): δ 20.9
29.6 (br, CH2 cod), 29.5 (d, JC‑Rh = 17.2, CH2 cod), 29.2 (d, JC‑Rh
=
11.8, CH2 cod).
[Rh2(nbd){μ-NH(CH2)3PPh2}2] (4). [Rh(μ-Cl)(nbd)]2 (100 mg,
0.217 mmol), Ph2P(CH2)3NH2 (106 mg, 0.434 mmol), KHDMS (88
mg, 0.441 mmol). Yield: 68%. Anal. Calcd. for C37H42N2P2Rh2: C,
56.79; H, 5.41; N, 3.58. Found: C, 56.77; H, 5.41; N, 3.57. MS (ESI+,
THF, m/z, %): 589.1 ([Rh(Ph2P(CH2)3NH2)2]+, 30), 438 ([Rh-
1
(nbd)(Ph2P(CH2)3NH2)]+, 100). H NMR (298 K, C6D6): δ 7.97
(m, 4H, Ph), 7.51 (m, 4H, Ph), 7.07−6.95 (m, 12H, Ph), 4.08 (br,
1H, CH nbd), 3.50 (br, 2H, CH nbd), 2.82 (m, 2H, CH2N), 2.19 (m,
2H, CH2N), 2.12 (m, 2H, CH2P), 1.90 (m, 2H, CH2), 1.78 (m, 2H,
CH2), 1.45 (br, 2H, CH nbd), 1.42 (br, 2H CH nbd), 1.60 (m,
1H, CH2 nbd), 1.28 (br, 1H, CH2 nbd + 2H, NH), 0.01 (m, 2H,
CH2P), 31P{1H} NMR (298 K, C6D6): δ 36.8 (d, JP‑Rh = 173.21).
13C{1H} NMR (298 K, C6D6): δ 138.3 (dd, JC‑P = 36.5, JC‑Rh = 5.6,
Ci), 133.8 (dt, JC‑P = 17.1, JC‑Rh = 5.9, Co), 128.3 (Cp), 126.9 (dd, JC‑P
(d, JP‑Rh = 171.8). 13C{1H} NMR (298 K, CD2Cl2): δ 134.6 (d, JC‑P
=
12.4, Co), 132.3 (Cp), 132.2 (d, JC‑P = 10.5, Co), 131.1 (Cp), 131.0 (d,
JC‑P = 9.6, Ci), 130.5 (d, JC‑P = 14.1, Ci), 130.0 (d, JC‑P = 10.2, Cm),
129.6 (d, JC‑Rh = 10.0, Cm), 92.0 (br, CH nbd), 90.8 (br, CH
nbd), 66.6 (dd, JC‑Rh = 4.9, JC‑P = 1.6, CH2 nbd), 63.0 (d, JC‑P = 12.0,
CH nbd), 59.7 (d, JC‑P = 9.5, CH nbd), 54.5 (d, JC‑P = 4.9,
= 8.5, JC‑Rh = 4.0, Cm), 60.5 (d, JC‑Rh = 5.5, CH2 nbd), 52.6 (d, JC‑Rh
=
CH2N), 53.3 (CH nbd), 53.1 (CH nbd), 38.7 (CH3), 24.3 (d, JC‑P
=
9.8, CH nbd), 52.3 (d, JC‑Rh = 10.3, CH nbd), 51.1 (br, CH
nbd), 49.1 (CH2N), 29.5 (CH2), 29.4 (d, JC‑P = 23.7, CH2P).
[Rh2(tfb){μ-NH(CH2)3PPh2}2] (5). [Rh(μ-Cl)(tfb)]2 (100 mg,
0.137 mmol), Ph2P(CH2)3NH2 (66.7 mg, 0.274 mmol), KHDMS
(56 mg, 0.281 mmol). Yield: 70%. Anal. Calcd. for C42H40F4N2P2Rh2:
C, 55.04; H, 4.40; N, 3.06. Found: C, 55.36; H, 4.18; N, 2.95. MS
24.8, CH2P), 20.7 (CH2).
[Rh(tfb){Ph2P(CH2)3NHMe}][BF4] (8). [Rh(μ-Cl)(tfb)]2 (100
mg, 0.137 mmol), AgBF4 (53.4 mg, 0.274 mmol), Ph2P(CH2)3NHMe
(70.6 mg, 0.274 mmol). Yield: 62%. Anal. Calcd. for
C28H26BF8NPRh: C, 49.96; H, 3.89; N, 2.08. Found: C, 50.08; H,
3.85; N, 2.08. MS (MALDI-Tof, CH2Cl2, m/z, %): 586.1 ([M]+,
1
(ESI+, THF, m/z, %): 589.1 ([Rh(Ph2P(CH2)3NH2)2]+, 100). H
1
100). ΛM (acetone, 5.0 × 10−4 M) = 44 Ω−1 cm2 mol−1. H NMR
NMR (298 K, C6D6): δ 7.91 (m, 4H, Ph), 7.51 (m, 4H, Ph), 7.11−
6.97 (m, 12H, Ph), 5.93 (br, 1H, CH tfb), 5.66 (br, 1H, CH tfb), 3.18
(m, 2H, CH tfb), 3.14 (m, 2H, CH tfb), 2.94 (m, 2H, CH2N),
2.19 (m, 2H, CH2), 2.01 (m, 2H, CH2N), 1.57 (m, 2H, CH2), 1.43
(m, 2H, CH2P), 1,09 (br, 2H, NH), 0.28 (m, 2H, CH2P). 31P{1H}
NMR (298 K, C6D6): δ 37.0 (d, JP‑Rh = 173.2). 19F NMR (298 K,
CDCl3): δ −148.73 (m, 2F, tfb), −149.58 (s, 4F, BF4), −161.81 (m,
2F, tfb). 13C{1H} NMR (298 K, CDCl3): δ 139.4 (d, JC‑F = 230.9, C-
(298 K, CD2Cl2): δ 7.90 (m, 2H, Ph), 7.70−762 (m, 3H, Ph), 7.51−
7.42 (m, 3H, Ph), 7.27 (m, 2H, Ph), 5.71 (br, 3H, CH tfb and CH
tfb), 5.41 (br, 1H, CH tfb), 4.32 (br, 1H, NH), 3.30 (s, 1H, CH
tfb), 3.13 (m, 1H, CH2N), 2.87 (m, 2H, CH tfb and CH2N), 2.55−
2.41 (m, 2H, CH2P), 2.38 (d, JH‑H = 6.0, 3H, CH3), 1.99 (m, 1H,
CH2), 1.79 (m, 1H, CH2). 31P NMR (298 K, CD2Cl2): δ 21.4 (d,
JP‑Rh = 172.0). 13C{1H} NMR (298 K, CD2Cl2): δ 140.3 (d, JC‑F
=
L
Organometallics XXXX, XXX, XXX−XXX