Mendeleev Commun., 2017, 27, 368–370
(a)
(b)
C(16)
C
H
H
C(17)
C(18)
C(15)
C(14)
C(13)
50
C(13)
C(4)
C(12)
C(11)
C(5)
60
C(20)
C(21)
C(22)
C(1)
C(2)
Fe(1)
C(3)
C(9)
70
P(1)
C(14)
C(11)
C(19)
C(26)
S(1)
C(5)
C(4)
C(3)
80
C(1)
C(2)
C(23)
C(24)
C(10)
90
C(12)
C(25)
C(30)
CH2
C(27)
C(28)
100
110
120
130
140
150
Fe(1)
C(8)
C(6)
C(7)
C(10)
C(6)
C(9)
C(29)
C(8)
C(7)
Figure 2 (a) Molecular structure of salt 3 (thermal ellipsoids drawn at the
50% probability level). Selected bond lengths (Å): Fe–C 2.035(5)–2.053(6)
〈2.044〉, C(1)–C(2) 1.443(7), C(1)–C(5) 1.436(7), C(2)–C(3) 1.421(7),
C(3)–C(4) 1.404(9), C(4)–C(5) 1.420(8), C(1)–C(11) 1.474(7), C(11)–C(12)
1.321(8), P(1)–C(11) 1.807(5); selected angles (°): C(12)–C(11)–C(1) 122.9(5),
C(12)–C(11)–P(1) 119.2(4), C(1)–C(11)–P(1) 117.9(4). (b) Molecular struc-
ture of salt 4 (thermal ellipsoids drawn at the 50% probability level).
Selected bond lengths (Å): Fe–C 2.030(2)–2.056(2) 〈2.039〉, C(1)–C(2)
1.435(3), C(1)–C(5) 1.432(3), C(2)–C(3) 1.417(3), C(3)–C(4) 1.414(3),
C(4)–C(5) 1.424(3), C(1)–C(11) 1.465(3), C(11)–C(12) 1.320(3), S(1)–C(11)
1.800(2); selected angles (°): C(12)–C(11)–C(1) 126.3(2), C(12)–C(11)–S(1)
120.8(2), C(1)–C(11)–S(1) 112.9(2).
C+
5.4 5.2 5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6 3.4
d/ppm
Figure 1 A fragment of the 2D-HMQC spectrum (600 MHz, DMF-d7) of
compounds 1, 2, and acetylferrocene.
experiments (Figure 1). The signals of the vinyl group in com-
pound 2 in the region characteristic of vinyl hydrogens2(a) are
observed (d 4.94 and 5.30 ppm) as the doublets (2J 2.0 Hz) and
have cross peaks with the carbon atoms of the vinyl group at
d 153.5 (–C+=) and 97.3 ppm (=CH2). For the 2D-HMBC and
2D-HMQC NMR spectra of salt 2, see Figure S1, S2, Online
Supplementary Materials.
A considerable stability of salt 2 in the Nafion solution allowed
us to speculate on the possible generation of cation 2 using the
Nafion film5 (sulfopolymer) as the protonating agent in super-
critical carbon dioxide (scCO2)3(e) followed by subsequent trans-
formations. scCO2 was chosen for having some advantages,6
i.e. the absence of gas–liquid mass transfer limitations, relatively
high rates of molecular diffusion and heat transfer, and the
possibility of molecular interactions with the dissolved reacting
species.7
0.01 Å in 4) and has a planar surrounding [the sum of the angles
at the C(11) atom in both compounds is 360.0°]. The C(1)–C(11)
and C(11)–C(12) bond lengths in both compounds virtually
coincide with the standard values of ordinary Csp2–Csp2 and double
Csp2=Csp2 bond lengths (1.478 and 1.321 Å),8 respectively. Thus,
one may state that there is neither contribution of the fulvene-
type structure in the cations nor additional coordination of the
exocyclic unsaturated fragment to the ferrocene iron atom.
Both compounds crystallize in the chiral space groups (P212121
for 3 and P21 for 4) and their absolute configurations were deter-
mined based on anomalous scattering. The compounds differ in
the orientation of the substituents at the C(11) atom relative to the
Cp ring of ferrocene [the C(2)–C(1)–C(11)–C(12) torsion angle
is 155.4° in 3 and 21.7° in 4].
Indeed, the reaction between compound 1 and the Nafion film
in scCO2 in the presence of PPh3 or SMe2 as the nucleophiles
resulted in new onium ferrocene derivatives, complexes 3 and 4
(see Scheme 1), isolated as the tetrafluoroborates in 76 and
85% yields, respectively. The molecular formulas of complexes
3 and 4 were elucidated by NMR spectroscopy‡ (1H, 13C, 31P,
This work was supported by the Russian Foundation for Basic
Research (grant no. 16-29-05334 ofi-m) and the RussianAcademy
of Sciences (programs P8, IP1 of the Presidium of the RAS).
11B, 2D-HSQC for 3 and H, 13C, 11B, 2D-HSQC for 4; see
Online Supplementary Materials
1
Online Supplementary Materials) along with the single crystal
X-ray diffraction analysis§ (Figure 2). The C(11) carbon atom is
in the plane of the Cp ligand (the deviation is 0.02 Å in 3 and
Supplementary data associated with this article can be found
in the online version at doi: 10.1016/j.mencom.2017.07.015.
References
‡
For 3: 1H NMR (CD2Cl2) d: 4.11 (m, 2H, C5H4), 4.21 (s, 5H, C5H5),
1 (a) N. C. Deno, in Carbonium Ions, eds. G. A. Olah and P. R. Schleyer,
John Wiley & Sons, New York, 1970, vol. 2, p. 783; (b) H. G. Richey, Jr.
and J. M. Richey, in Carbonium Ions, eds. G. A. Olan and P. R. Schleyer,
John Wiley & Sons, New York, 1970, vol. 2, p. 899.
2 (a) T. S. Abram and W. E. Watts, J. Chem. Soc., Perkin Trans. 1, 1977,
1522; (b) T. S. Abram and W. E. Watts, J. Chem. Soc., Perkin Trans. 1,
1977, 1527; (c) T. S.Abram and W. E. Watts, J. Chem. Soc., Perkin Trans. 1,
1977, 1532.
trans
3
3
6.16 (d, 1H, =CH2, JHP 16.0 Hz), 7.25 (d, 1H, =CH2, JHP 36.0 Hz),
7.6–7.7 (m, 6H, o-HPh), 7.7–7.8 (m, 6H, m-HPh), 7.93 (t, 1H, 3H, p-HPh
,
3JHH 6.4 Hz). 13C NMR (CD2Cl2) d: 70.1 (2C, C5H4), 70.3 (2C, C5H4,
3JCP 3.2 Hz), 70.49 (5C, C5H5), 81.5 (Ci, C5H4, JCP 13.1 Hz), 117.2
2
(–CP+=, JCP 30.4 Hz), 130.4 (6C, m-CPh
,
3JCP 10.1 Hz), 131 (3C,
1
1
2
i-CPh, JCP 59.4 Hz) 134.4 (6C, o-CPh, JCP 8.0 Hz), 135.6 (3C, p-CPh
,
4JCP 2.3 Hz), 139.9 (=CH2, JCP 8.0 Hz). 31P NMR (CD2Cl2) d: 22.19.
11B NMR (CD2Cl2) d: –1.12, see Figures S3–S7, Online Supplementary
Materials.
2
Crystal data for 4·BF4–: C14H17F4SBFe, M = 359.99, dark red crystals,
monoclinic, space group P21, a = 7.3644(4), b = 10.3950(6) and c =
= 9.9962(6) Å, b = 92.161(1)°, V = 764.69(8) Å3, dcalc = 1.563 g cm3,
Z = 2, m(MoKa) = 11.52 cm–1, T = 120(2) K, 2qmax = 60°, R1 = 0.0332
for 3768 reflections with I > 2s(I), and wR2 = 0.0572 for all 4446 unique
reflections (Rint = 0.0356). Flack parameter 0.023(17).
Crystal data were collected with a Bruker SMART APEX II diffrac-
tometer [l(MoKa) = 0.71073 Å]. All calculations were performed using
SHELXTL program package.9
1
For 4: H NMR (CD2Cl2) d: 3.13 (6H, Me), 4.33 (5H, C5H5), 4.58
(4H, C5H4), 6.24 (H, =CH2, 2JHH 2.4 Hz), 6.48 (H, =CH2, 2JHH 2.4 Hz).
13C NMR (CD2Cl2) d: 27.7 (2C, Me), 68.4 (2C, C5H4), 70.5 (5C, C5H5),
71.2 (2C, C5H4), 78.09 (Ci, C5H4), 123.3 (=CH2), 136.1 (–CS+=). 11B NMR
(CD2Cl2) d: –1.1, see Figures S8–S11, Online Supplementary Materials.
Crystal data for 3·BF4–: C30H26F4BPFe, M = 560.14, dark red crystals,
§
orthorhombic, space group P212121, a = 9.5948(6), b = 16.1709(10)
and c = 16.2431(10) Å, V = 2520.2(3) Å3, dcalc = 1.476 g cm–3, Z = 4,
m(MoKa) = 7.10 cm–1, T = 120(2) K, 2qmax = 56°, R1 = 0.0611 for 5169
reflections with I > 2s(I), and wR2 = 0.1213 for all 6038 unique reflections
(Rint = 0.0763). Flack parameter 0.05(3).
CCDC 1523012 and 1523013 contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge from The
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