Article
Organometallics, Vol. 29, No. 21, 2010 5659
orange-red to off-white occurred. The solution was concentrated to
ca. 5 mL in vacuo, and pentane (30 mL) was added. A colorless solid
precipitated, from which the solution was decanted. The solid residue
was washed three times with pentane (5 mL each) and dried in vacuo
for 15 min at 0 °C: yield 465 mg (73%); mp 83 °C dec. Anal. Calcd for
C10H12F3O4RhS: C, 30.94; H, 3.12; S, 8.26. Found: C, 30.61; H, 3.00;
S, 8.06. IR (CH2Cl2): ν(CO) 2096, ν(OSOasym) 1260, ν(CFsym) 1250,
4 H, H of CH2 cis to dCCH3), 1.85 (s, 12 H, dCCH3), 1.68 (d,
2J(H,H) = 1.7 Hz, 4 H, H ofCH2 trans to dCCH3), 1.63 (br s, 9 H,
NCCH3). 13C NMR (100.6 MHz, CD2Cl2):
δ 141.6 (dt,
1J(Rh,C) = 71.7, 1J(14N,C) = 17.1 Hz, CN), 121.2 (q, 1J(F,C) =
1
320.9 Hz, CF3), 108.5 (d, J(Rh,C) = 4.1 Hz, CHCH3), 60.1 (t,
1J(14N,C) = 4.6 Hz, NCCH3), 51.4 (d, 1J(Rh,C) = 9.2 Hz,
CH2dCCH3), 30.8 (s, NCCH3), 17.6 (s, dCCH3). 19F NMR
(376.4 MHz, CD2Cl2): δ -78.6 (s).
ν(CFasym) 1163, ν(OSOsym) 1031 cm-1
.
1H NMR (400 MHz,
3
acetone-d6): δ 6.27 (m, 4 H, CH2dCHCHdCH2), 3.63 (d, J(H,
H) = 7.0 Hz, 4 H, H of CH2 cis to dCH), 2.80 (d, 3J(H,H) = 10.0
Hz, 4 H, H of CH2 trans to dCH). 13C NMR (100.6 MHz, acetone-
d6): δ 197.1 (d, 1J(Rh,C) = 77.6 Hz, CO), 121.5 (q, 1J(F,C) = 328.0
Hz, CF3),96.1(d,1J(Rh,C) =3.8Hz,CH2dCHCHdCH2),56.3(d,
1J(Rh,C) = 7.6 Hz, CH2dCHCHdCH2). 19F NMR (376.4 MHz,
acetone-d6): δ -78.4 (s).
Preparation of [Rh(s-cis-η4-C4H6)2(CN-2,6-C6H3iPr2)]CF3-
SO3 (37). This compound was prepared as described for 26
from 2 (57 mg, 0.15 mmol) and CN-2-C6H3iPr2 (40 μL, 0.16
mmol). A colorless solid was obtained: yield 82 mg (95%); mp 69
°C dec. Anal. Calcd for C22H29F3NO3RhS: C, 48.27; H, 5.33; N,
2.55; S, 5.85. Found: C, 47.98; H, 5.02; N, 2.46; S, 5.99. IR
(CH2Cl2): ν(CN) 2172, ν(OSOasym) 1275, ν(CFsym) 1253,
Preparation of (Rh(s-cis-η4-C4H6)2(CNtBu)]CF3SO3 (34).
This compound was prepared as described for 26 from 2 (44
mg, 0.12 mmol) and CNtBu (14 μL, 0.12 mmol). A colorless
solid was obtained: yield 53 mg (98%); mp 67 °C dec. Anal.
Calcd for C14H21F3NO3RhS: C, 37.93; H, 4.77; N, 3.16; S, 7.23.
Found: C, 37.54; H, 4.47; N, 3.47; S, 6.80. IR (CH2Cl2): ν(CN)
2196, ν(OSOasym) 1275, ν(CFsym) 1255, ν(CFasym) 1170,
ν(CFasym) 1172, ν(OSOsym) 1031 cm-1. H NMR (200 MHz,
1
CD2Cl2): δ 7.50 (m, 1 H, p-H of C6H3), 7.33 (m, 2 H, m-H of
C6H5), 6.06 (m, 4 H, CH2dCHCHdCH2), 3.38 (d, 3J(H,H) =
7.1 Hz, 4 H, H of CH2 cis to dCH), 3.37 (sept, 3J(H,H) = 6.9
Hz, 2 H, CHCH3), 2.05 (d, 3J(H,H) = 9.9 Hz, 4 H, H of CH2
trans to dCH), 1.37 (d, 3J(H,H) = 6.9 Hz, 6 H, CHCH3). 13
C
NMR (50.3 MHz, CD2Cl2): 145.8 (s, o-C of C6H3), 131.4 (s, p-C
of C6H5), 124.3 (s, m-C of C6H5), 121.4 (q, 1J(F,C) = 321.5 Hz,
CF3), 92.4 (d, 1J(Rh,C) = 3.5 Hz, CH2dCHCHdCH2), 52.4 (d,
1J(Rh,C) = 7.7 Hz, CH2dCHCHdCH2), 30.8 (s, CHCH3),
22.6 (s, CHCH3); signals of ipso-C of C6H3 and CN not exactly
located. 19F NMR (376.4 MHz, CD2Cl2): δ -78.7 (s).
1
ν(OSOsym) 1031 cm-1. H NMR (400 MHz, CD2Cl2): δ 5.85
(m, 4 H, CH2dCHCHdCH2), 3.22 (d, 3J(H,H) = 6.5 Hz, 4 H,
H of CH2 cis to dCH), 1.90 (d, 3J(H,H) = 9.7 Hz, 4 H, H of CH2
trans to dCH), 1.68 (s, CCH3). 13C NMR (100.6 MHz, CD2Cl2):
δ 139.9 (dt, 1J(Rh,C) = 75.3, 1J(14N,C) = 17.8 Hz, CN), 121.3
(q, 1J(F,C) = 321.4 Hz, CF3), 91.7 (d, 1J(Rh,C) = 4.1 Hz,
CH2dCHCHdCH2), 60.3 (t, 1J(14N,C) = 4.6 Hz, CCH3), 52.4
Preparation of [Rh(s-cis-η4-C4H5Me)2(CN-2,6-C6H3iPr2)]-
CF3SO3 (38). This compound was prepared as described for
26 from 3 (85 mg, 0.22 mmol) and CNtBu (25 μL, 0.22 mmol). A
1
(d, J(Rh,C) = 7.1 Hz, CH2dCHCHdCH2), 30.6 (s, CCH3).
19F NMR (376.4 MHz, CD2Cl2): δ -78.7 (s).
colorless solid was obtained, which according to the 1H and 13
C
Preparation of [Rh(s-cis-η4-C4H5Me)2(CNtBu)]CF3SO3 (35).
This compound was prepared as described for 26 from 3 (85 mg,
0.22 mmol) and CNtBu (25 μL, 0.22 mmol). A colorless solid
was obtained, which according to the 1H and 13C NMR spectra
consists of a 4:1 mixture of the anti and syn isomers: yield 95 mg
(92%); mp 101 °C dec. Anal. Calcd for C16H25F3NO3RhS: C,
40.77; H, 5.34; N, 2.97; S, 6.80. Found: C, 40.46; H, 4.97; N,
3.24; S, 6.43. IR (CH2Cl2): ν(CN) 2195, ν(OSOasym) 1275,
NMR spectra consists of a 4:1 mixture of the anti and syn
isomers: yield 95 mg (92%); mp 101 °C dec. Anal. Calcd for
C16H25F3NO3RhS: C, 40.77; H, 5.34; N, 2.97; S, 6.80. Found: C,
40.46; H, 4.97; N, 3.24; S, 6.43. IR (CH2Cl2): ν(CN) 2195,
ν(OSOasym) 1275, ν(CFsym) 1254, ν(CFasym) 1171, ν(OSOsym
)
1
1032 cm-1. H NMR (400 MHz, CD2Cl2): anti isomer, δ 5.04
3
(dd, J(H,H) = 10.6 and 7.4 Hz, 2 H, CH2dCHCCH3), 3.27
(dd, 3J(H,H) = 7.4, 2J(H,H) = 2.0 Hz, 2 H, H of CH2 cis
to dCH), 3.09 (s, 2 H, H of CH2 trans to dCCH3), 2.19 (s, 6
H, dCCH3), 1.82 (d, 3J(H,H) = 10.6 Hz, 2 H, H of CH2 trans
to dCH), 1.65 (br s, 11 H, NCCH3 and H of CH2 cis to dCCH3);
syn isomer, δ 5.57 (m, 2 H, CH2dCHCCH3), 3.16 (s, 2 H, H of
CH2 trans to dCCH3), 3.05 (br d, 3J(H,H) = 7.2 Hz, 2 H, H of
CH2 cis to dCH), 1.95 (s, 6 H, CCH3), 1.67 (br d, 3J(H,H) =
10.6 Hz, 2 H, H of CH2 trans to dCH), 1.51 (br s, 9 H, NCCH3),
1.47 (s, 2 H, H of CH2 cis to dCCH3). 13C NMR (100.6 MHz,
CD2Cl2): anti isomer, δ 139.8 (dt, 1J(Rh,C) = 73.2, 1J(14N,C) =
ν(CFsym) 1254, ν(CFasym) 1171, ν(OSOsym) 1032 cm-1
.
1H
3
NMR (400 MHz, CD2Cl2): anti isomer, δ 5.04 (dd, J(H,H) =
10.6 and 7.4 Hz, 2 H, CH2dCHCCH3), 3.27 (dd, 3J(H,H) = 7.4,
2J(H,H) = 2.0 Hz, 2 H, H of CH2 cis to dCH), 3.09 (s, 2 H, H of
CH2 trans to dCCH3), 2.19 (s, 6 H, dCCH3), 1.82 (d, 3J(H,H) =
10.6 Hz, 2 H, H of CH2 trans to dCH), 1.65 (br s, 11 H, NCCH3
and H of CH2 cis to dCCH3); syn isomer, δ 5.57 (m, 2 H,
CH2dCHCCH3), 3.16 (s, 2 H, H of CH2 trans to dCCH3), 3.05
(br d, 3J(H,H) = 7.2 Hz, 2 H, H of CH2 cis to dCH), 1.95 (s, 6 H,
3
1
CCH3), 1.67 (br d, J(H,H) = 10.6 Hz, 2 H, H of CH2 trans
17.0 Hz, CN), 121.4 (q, J(F,C) = 321.5 Hz, CF3), 111.8 (d,
1J(Rh,C) = 4.1 Hz, CHCH3), 98.9 (d, 1J(Rh,C) = 5.1 Hz, CHd
CH2), 60.2 (t, 1J(14N,C) = 4.6 Hz, NCCH3), 51.4 (d, 1J(Rh,C) =
to dCH), 1.51 (br s, 9 H, NCCH3), 1.47 (s, 2 H, H of CH2 cis
to dCCH3). 13C NMR (100.6 MHz, CD2Cl2): anti isomer, δ 139.8
(dt, 1J(Rh,C) = 73.2, 1J(14N,C) = 17.0 Hz, CN), 121.4 (q, 1J(F,
C) = 321.5 Hz, CF3), 111.8 (d, 1J(Rh,C) = 4.1 Hz, CHCH3),
98.9 (d, 1J(Rh,C) = 5.1 Hz, CHdCH2), 60.2 (t, 1J(14N,C) = 4.6
1
8.1 Hz, CH2dCCH3), 49.5 (d, J(Rh,C) = 8.1 Hz, CH2dCH),
30.6 (s, NCCH3), 21.9 (s, dCCH3); syn isomer, δ 113.0 (d, 1J(Rh,
C) = 3.9 Hz, CHCH3), 90.1 (d, 1J(Rh,C) = 4.8 Hz, CHdCH2),
58.5 (t, 1J(14N,C) = 5.0 Hz, NCCH3), 52.0(d, 1J(Rh,C) = 8.5Hz,
1
Hz, NCCH3), 51.4 (d, J(Rh,C) = 8.1 Hz, CH2dCCH3), 49.5
(d, 1J(Rh,C) = 8.1 Hz, CH2dCH), 30.6 (s, NCCH3), 21.9
(s, dCCH3); syn isomer, δ 113.0 (d, 1J(Rh,C) = 3.9 Hz, CHCH3),
90.1 (d, 1J(Rh,C) = 4.8 Hz, CHdCH2), 58.5 (t, 1J(14N,C) = 5.0
1
CH2dCCH3), 50.1 (d, J(Rh,C) = 9.1 Hz, CH2dCH), 30.4 (s,
NCCH3), 20.3 (s, dCCH3), other signals of syn isomer not exactly
located. 19F NMR (376.4 MHz, CD2Cl2): δ -78.7 (s).
1
Preparation of [Rh(s-cis-η4-C4H4Me2)2(CN-2,6-C6H3iPr2)]-
CF3SO3 (39). This compound was prepared as described for
26 from 4 (76 mg, 0.18 mmol) and CN-2,6-C6H3iPr2 (42 μL, 0.18
mmol). A colorless solid was obtained: yield 108 mg (98%); mp
120 °C dec. Anal. Calcd for C26H35F3NO3RhS: C, 51.91; H,
5.86; N, 2.32; S, 5.33. Found: C, 51.57; H, 5.68; N, 2.45; S, 5.12.
IR (CH2Cl2): ν(CN) 2163, ν(OSOasym) 1278, ν(CFsym) 1253,
Hz, NCCH3), 52.0 (d, J(Rh,C) = 8.5 Hz, CH2dCCH3), 50.1
(d, 1J(Rh,C) = 9.1 Hz, CH2dCH), 30.4 (s, NCCH3), 20.3
(s, dCCH3), other signals of syn isomer not exactly located.
19F NMR (376.4 MHz, CD2Cl2): δ -78.7 (s).
Preparation of [Rh(s-cis-η4-C4H4Me2)2(CNtBu)]CF3SO3 (36).
This compound was prepared as described for 26 from 4 (142 mg,
0.34 mmol) and CNtBu (42 μL, 0.35 mmol). A colorless solid was
obtained: yield 138 mg (81%); mp 130 °C dec. Anal. Calcd for
C18H29F3NO3RhS: C, 43.29; H, 5.85; N, 2.80; S, 6.42. Found: C,
42.90; H, 5.42; N, 2.82; S, 6.25. IR (CH2Cl2): ν(CN) 2190,
ν(OSOasym) 1275, ν(CFsym) 1250, ν(CFasym) 1171, ν(OSOsym) 1031
cm-1. 1H NMR (400 MHz, CD2Cl2): δ 3.03 (d, 2J(H,H) = 1.7 Hz,
1
ν(CFasym) 1170, ν(OSOsym) 1031 cm-1. H NMR (400 MHz,
CD2Cl2): δ 7.48 (m, 1 H, p-H of C6H3), 7.31 (m, 2 H, m-H of
C6H5), 3.31 (sept, J(H,H) = 7.0 Hz, 2 H, CHCH3), 3.21 (d,
3
2J(H,H) = 1.4 Hz, 4 H, H of CH2 cis to dCCH3), 1.94 (s,
12 H, dCCH3), 1.84 (s, 4 H, H of CH2 trans to dCCH3), 1.35 (d,