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A.M. FitzGerald et al. / Journal of Organometallic Chemistry 584 (1999) 206–212
208
Table 1
Analytical and NMR data for compounds 1–7
Compound
Analysis (%)a
w(CꢀNR)
(cm−1 b
NMRc
)
1
C, 58.0 (58.2); H, 5.1 (5.1)
1H: 7.88 (m, 6H, C6H5), 7.38 (m, 9H, C6H5), 4.26 (s, 1H,
4
4
C5Me4H), 1.71 (d, JP–H 4.8, 6H, Me), 1.13 (d, JP–H 1.2, 6H, Me).
1
31P{1H}: 31.4 (dm, JRh–P 142)
2
C, 49.5 (50.1); H, 3.2 (3.6)
1H: 7.84 (m, 4H, C6H5), 7.32 (m, 6H, C6H5), 4.62 (s, 1H, C5H),
4
4
1.69 (d, JP–H 5.7, 6H, Me), 1.23 (d, JP–H 0.7, 6H, Me). 19F:
3
−120.59 (m, 2F, Fortho), −148.49 (t, JF–F 20.5, 1F, Fpara), −
1
159.53 (m, 2F, Fmeta).31P{1H}: 21.4 (dm, JRh–P 147)
3
C, 46.85 (47.55); H, 6.0; N
3.3 (3.5)
2214
2216
1H: 5.00 (1H, s, C5H), 3.99 (1H, m, CNCH), 1.97 (2H, m, C6H11),
1.84 (6H, s, Me), 1.79 (6H, s, C6H11), 1.54 (6H, d, JRh–H 1.7, Me),
3
1.42 (2H, s, C6H11
)
4d
C, 55.0 (54.6); H, 4.9 (5.3);
N 2.1 (1.8)
1H: 7.51 (A2B2CM spin system, 15H), 5.31 (s, CH2Cl2), 5.09 (1H,
4
s, C5Me4H), 3.86 (1H, m, CNCH), 1.93 (3H, d, JP–H 3.6, Me),
4
1.87 (3H, d, JP–H 5.8, Me), 1.80 (2H, m, C6H11), 1.55 (3H, d,
3JRh–H 0.8, Me), 1.49 (4H, m, C6H11), 1.22 (4H, m, C6H11), 1.19
4
(3H, d, JP–H 5.9, Me). 19F: −153.19 and −153.25 (2s, 1:4, 4F,
BF−4
)
5e
C, 49.2 (49.6); H, 4.5 (4.2);
N 1.6 (1.7)
2214
2222
1H: 7.72 (2H, m, PPh2), 7.58 (8H, m, PPh2), 5.30 (s, CH2Cl2), 5.21
4
(1H, s, C5Me4H), 3.81 (1H, m, CNCH), 1.91 (3H, d, JP–H 6.1,
4
Me), 1.82 (3H, d, JP–H 3.5, Me), 1.78 (2H, m, C6H11), 1.76 (3H,
4
3
d, JP–H 2.6, Me), 1.45 (4H, m, C6H11), 1.39 (3H, d, JRh–H, 5.0
Me), 1.27 (4H, m, C6H11). 19F: −123. 59 (2F, d, JF–F 19.0,
3
Fortho), −144.78 (1F, m, Fpara), −153.26 and −153.32 (2s, 1:4, 4F,
1
BF−4 ), −159.54 (2F, m, Fmeta). 31P{1H}: 24.5 (d, JRh–P 131)
6
C, 49.2 (48.9); H, 6.4 (6.2);
N 4.2 (5.0)
1H: 5.78 (1H, s, C5Me4H), 4.15 (2H, m, CNCH), 2.00 (6H, s, Me),
1.88 (6H, s, Me), 1.78 (8H, m, C6H11), 1.52 (12H, m, C6H11). 19F:
−153.21 and −153.27 (2s, 1:4, 4F, BF4)
7f
C, 54.7 (54.9); H, 5.1 (4.9)
1H: 7.70 (m, 2H, Hp), 7.45 (m, 14H, C6H5), 7.28 (m, 4H, C6H5),
5.48 (s, 1H, C5H), 3.32 (m, 2H, PCH2), 2.36 (m, 2H, PCH2), 1.19
(s, 6H, Me), 0.95 (s, 6H, Me).g 19F: −152.23 and −152.29 (2s, 1:4,
1
4F, BF4).g 31P{1H}: 23.7 (dm, JRh–P 138)g
a Required values are given in parentheses.
b KBr disc
c Unless stated otherwise recorded in CDCl3 at 298 K.
d Crystallized with 0.5 CH2Cl2.
e Crystallized with 0.25 CH2Cl2.
f Crystallized with 0.33 CH2Cl2.
g Recorded in (CD3)2CO.
sodium tetrafluoroborate yielded the bis(isocyanide)
complex [(h5-C5Me4H)RhCl(CNC6H11)2]+·BF4− (6).
The analytical and NMR spectroscopic data of 4–6
(Table 1) are entirely consistent with these formula-
tions. The H-NMR spectra of 4 and 5 display four
methyl resonances due to the chirality at the rhodium
(PPh3)(CNC6H11)]+·BPh4− and [(h5-C5Me4H)RhCl-
(CNC6H11)2]+·BPh4−, respectively [6].
Treatment of [(h5-C5Me4H)RhCl(m-Cl)]2 with NaBF4
in methanol, followed by addition of dppe in
dichloromethane gave the salt [(h5-C5Me4H)RhCl-
(dppe)]+·BF4− 7 in 69% yield (Scheme 1). The salt was
characterized by elemental analysis and NMR spec-
troscopy (Table 1). In contrast to the salts 4 and 5,
coupling between the phosphorus atoms and the hydro-
gen atoms of the tetramethylcyclopentadienyl group is
not observed, and the three resonances appear as sin-
glets at l 5.48, 1.19 and 0.95. The 31P{1H}-NMR
spectrum shows a doublet resonance at l 23.7 with a
1
atom. All these resonances show coupling to phospho-
4
rus. For both salts there are two resonances with ꢀ JP–H
ꢀ
of ca. 6 Hz, one with a coupling of ca. 3.5, and the
other has a coupling of 0.8 for 4 and 2.6 Hz for 5. The
phosphine complexes 4 and 5 exhibit w(CN) at ca. 2215
and 6 at 2222 cm−1, which are comparable with those
of 2210 and 2212 cm−1 for [(h5-C5Me4H)RhCl-