Full Paper
doi.org/10.1002/ejic.202000414
EurJIC
European Journal of Inorganic Chemistry
1′-Triphenylsilyl-1-(2-(E)-phenylvinyl)-2-(diphenyl-phosphino)-
ferrocene (4d). Compound 4d was synthesized according to the
general procedure using diethyl benzylphosphonate (0.11 g,
0.47 mmol) and 3d (0.10 g, 0.16 mmol). After evaporation of all
volatiles 4d was obtained as a dark orange solid.
4.29 (m, 1H, C5H4), 4.42–4.45 (m, 1H, C5H4), 4.50–4.52 (m, 1H, C5H3),
6.61 (d, 3JH,H = 16.1 Hz, 1H, CHPh), 7.06–7.14 (m, 3H, CHCHPh, PPh),
7.16–7.24 (m, 4H, CHPh, PPh), 7.27–7.35 (m, 4H, CHPh, SiPh), 7.35–
7.44 (m, 9H, PPh, CHPh, SiPh), 7.56 (dt, JH,H = 1.5, 7.9 Hz, 2H, PPh),
7.60 (dd, JH,H = 1.2, 8.0 Hz, 2H, SiPh), 7.71 (dd, JH,H = 1.2, 7.9 Hz, 2H,
SiPh). 13C{1H} NMR (CDCl3, δ): 18.4 (qC(CH3)3), 28.0 (CH3), 67.8
Yield 94 mg (0.13 mmol, 82 % based on 3d). Anal. calcd. for
3
2
(qC5H4), 68.7 (d, JP, C = 3.0 Hz, C5H3), 72.5 (C5H3), 73.2 (d, JP, C
=
C
28H24Fe (416.34 g/mol): C, 78.90; H, 5.38; found C, 78.58; H, 5.61.
1
3.6 Hz, C5H3), 73.9 (d, JP, C = 2.6 Hz, C5H4), 75.9 (d, JP, C = 8.9 Hz,
Mp. 93 °C. 1H NMR (CDCl3, δ): 3.58–3.61 (m, 1H, C5H3), 3.76 (ddd,
qC5H3), 76.0 (C5H4), 76.2 (d, JP, C = 1.6 Hz, C5H4), 78.0 (C5H4), 89.0 (d,
3JH,H = 2.1 Hz, JH,H = 1.0, 1.0 Hz, 1H, C5H4), 3.88 (dd, JH,H = 2.5,
2.5 Hz, 1H, C5H3), 4.29 (ddd, JH,H = 2.3 Hz, JH,H = 1.1, 1.1 Hz, 1H,
C5H4), 4.32 (ddd, JH,H = 2.3, 2.3 Hz, JH,H = 1.1 Hz, 1H, C5H4), 4.45
(ddd, JH,H = 2.4, 2.4 Hz, JH,H = 1.1 Hz, 1H, C5H4), 4.49–4.52 (m, 1H,
4
3
2JP, C = 21.3 Hz, qC5H3), 125.5 (d, JP, C = 11.8 Hz, CHCHPh), 126.5
3
3
4
4
(CHPh), 127.3 (CHPh), 127.8 (SiPh), 127.9 (SiPh), 128.1 (d, JP, C
=
3
4
3
1.7 Hz, CHPh), 128.2 (PPh), 128.5 (d, JP, C = 6.0 Hz, PPh), 128.6 (d,
3
4
3JP, C = 7.7 Hz, PPh), 129.0 (CHPh), 129.5 (SiPh), 129.6 (SiPh), 129.8
3
C5H4), 6.63 (d, JH,H = 16.1 Hz, 1H, CHPh), 7.07–7.13 (m, 3H, PPh,
2
2
(PPh), 132.5 (d, JP, C = 17.4 Hz, PPh), 135.8 (d, JP, C = 21.1 Hz, PPh),
CHCHPh), 7.16–7.23 (m, 4H, PPh, ChPh), 7.29 (t, JH,H = 7.4 Hz, 8H,
CHPh, SiPh), 7.35–7.43 (m, 8H, PPh, CHPh, SiPh), 7.47–7.51 (m, 6H,
SiPh), 7.53–7.58 (m, 2H, PPh). 13C{1H} NMR (CDCl3, δ):= 67.4 (qC5H4),
68.7 (d, 3JP, C = 3.2 Hz, C5H3), 72.3 (C5H3), 73.2 (d, 2JP, C = 3.4 Hz, C5H3),
74.4 (d, JP, C = 2.3 Hz, C5H4), 75.5 (C5H4), 76.3 (d, 1JP, C = 9.1 Hz, qC5H3),
136.0 (qSiPh), 136.1 (qSiPh), 136.8 (SiPh), 136.9 (SiPh), 137.6 (d, 1JP, C
=
8.5 Hz, PPh), 138.3 (qCHPh), 140.3 (d, JP, C = 10.1 Hz, PPh). 31P{1H}
NMR (CDCl3, δ): –23.3 (s). HRMS: m/z: calcd. for C46H43FePSi:
710.2221, found 710.2164 [M]+.
q
1
q
2
1′-(Tributyltin)-1-(2-(E)-phenylvinyl)-2-(diphenylphosphino)fer-
rocene (4g). Compound 4g was synthesized according to the gen-
eral procedure using diethyl benzylphosphonate (0.27 g,
1.20 mmol) and 3g (0.27 g, 0.40 mmol). After evaporation of all
volatiles in vacuo 4g was obtained as an dark orange oil.
76.5 (d, JP, C = 1.6 Hz, C5H4), 78.0 (C5H4), 89.2 (d, JP, C = 21.0 Hz,
3
qC5H3), 125.4 (d, JP, C = 11.6 Hz, CHCHPh), 126.6 (CHPh), 127.4
(CHPh), 128.1 (CHPh, SiPh), 128.2 (PPh), 128.6 (d, 3JP, C = 5.7 Hz, PPh),
128.7 (d, 3JP, C = 8.0 Hz, PPh), 129.0 (CHPh), 129.8 (PPh), 129.9 (SiPh),
2
2
132.5 (d, JP, C = 17.4 Hz, PPh), 135.8 (d, JP, C = 21.3 Hz, PPh), 135.9
(qSiPh), 136.4 (SiPh), 137.6 (d, JP, C = 8.7 Hz, qPPh), 138.2 (qCHPh),
1
Yield 248 mg (0.33 mmol, 82 % based on 3g). 1H NMR (CDCl3, δ):
0.87 (t, 3JH,H = 7.3 Hz, 9H, CH3), 0.90–0.95 (m, 6H, SnCH2), 1.29 (sext,
3JH,H = 7.3 Hz, 6H, CH2CH3), 1.44–1.51 (m, 6H, CH2CH2CH3), 3.60–
3.64 (m, 1H, C5H4), 3.80–3.82 (m, 1H, C5H3), 4.01–4.04 (m, 1H, C5H4),
1
140.2 (d, JP, C = 10.1 Hz, qPPh). 31P{1H} NMR (CDCl3, δ): –23.5 (s).
HRMS: m/z: calcd. for C48H39FePSi: 730.1908, found 730.1835 [M]+.
1′-Triisopropylsilyl-1-(2-(E)-phenylvinyl)-2-(diphenylphos-
phino)ferrocene (4e). Compound 4e was synthesized according to
the general procedure using diethyl benzylphosphonate (0.23 g,
0.99 mmol) and 3e (0.21 g, 0.33 mmol). After evaporation of all
volatiles 4e was obtained as a dark orange solid.
3
4
4.23 (ddd, JH,H = 2.2, 2.2 Hz, JH,H = 0.9 Hz, 1H, C5H4), 4.33 (dd,
3JH,H = 2.5, Hz, 1H, C5H3), 4.33–4.36 (m, 1H, C5H4), 4.76–4.79 (m, 1H,
C5H3), 6.75 (d, 3JH,H = 16.1 Hz, 1H, CHPh), 7.13–7.24 (m, 7H, CHCHPh,
PPh), 7.28 (t, JH,H = 7.8 Hz, 2H, CHPh), 7.38 (d, JH,H = 7.4 Hz, 2H,
CHPh), 7.39–7.43 (m, 3H, PPh), 7.58–7.63 (m, 2H, PPh). 13C{1H} NMR
(CDCl3, δ): 10.3 (SnCH2), 13.8 (CH3), 27.5 (3J119Sn,13C = 57.4 Hz,
Yield 198 mg (0.31 mmol, 94 % based on 3e). Anal. calcd. for
3
CH2CH3), 29.3 (2J119Sn,13C = 19.9 Hz, CH2CH2CH3), 67.7 (d, JP, C
=
C
28H24Fe (416.34 g/mol): C, 74.51; H, 7.21; found C, 74.32; H, 7.34.
1
3
3.0 Hz, C5H3), 70.3 (qC5H4), 70.9 (C5H3), 72.4 (d, JP, C = 3.4 Hz, C5H3),
2
Mp. 60 °C. H NMR (CDCl3, δ): 1.00 (d, JH,H = 7.2 Hz, 9H, CH3), 1.03
(d, 3JH,H = 7.2 Hz, 9H, CH3), 1.06–1.16 (m, 3H, CH), 3.67 (ddd, 3JH,H
2.2 Hz, 4JH,H = 1.0, 1.0 Hz, 1H, C5H4), 3.84 (ddd, 3JH,H = 2.3 Hz, 4JH,H
=
=
=
73.0 (d, JP, C = 1.8 Hz, C5H4), 75.2 (d, JP, C = 1.3 Hz, C5H4), 75.3 (C5H4),
1
2
76.0 (d, JP, C = 9.0 Hz, qC5H3), 77.7 (C5H4), 88.7 (d, JP, C = 21.0 Hz,
3
3
4
qC5H3), 125.7 (d, JP, C = 12.4 Hz, CHCHPh), 126.2 (CHPh), 127.0
3
1.1 Hz, JP, H = 1.1 Hz, 1H, C5H3), 4.19 (ddd, JH,H = 2.2 Hz, JH,H
1.0, 1.0 Hz, 1H, C5H4), 4.31 (ddd, JH,H = 2.3, 2.3 Hz, JH,H = 1.1 Hz,
3
4
4
3
(CHPh), 127.2 (d, JP, C = 1.4 Hz, CHPh), 127.9 (PPh), 128.3 (d, JP, C
=
3
4
5.7 Hz, PPh), 128.4 (d, 3JP, C = 7.7 Hz, PPh), 128.7 (CHPh), 129.4 (PPh),
1H, C5H4), 4.36 (ddd, JH,H = 2.3, 2.3 Hz, JH,H = 1.1 Hz, 1H, C5H4),
4.41 (dd, 3JH,H = 2.5, 2.5 Hz, 1H, C5H3), 4.83–4.86 (m, 1H, C5H3), 6.75
(d, 3JH,H = 16.1 Hz, 1H, CHPh), 7.13–7.24 (m, 7H, PPh, CHCHPh), 7.29
(t, 3JH,H = 7.6 Hz, 2H, CHPh), 7.36–7.44 (m, 5H, PPh, CHPh), 7.58–7.65
(m, 2H, PPh). 13C{1H} NMR (CDCl3, δ): 11.6 (CH), 18.6 (CH3), 18.7
2
2
132.2 (d, JP, C = 17.5 Hz, PPh), 135.5 (d, JP, C = 21.5 Hz, PPh), 137.4
(d, JP, C = 9.1 Hz, qPPh), 137.9 (qCHPh), 140.1 (d, JP, C = 10.2 Hz,
qPPh). 31P{1H} NMR (CDCl3, δ): –22.0 (s). 119Sn{1H} NMR (CDCl3, δ):
–19.4 (s). HRMS: m/z: calcd. for C42H52FePSn: 762.2100, found
762.2075 [M]+.
1
1
(CH3), 68.2 (d, JP, C = 3.0 Hz, C5H3), 69.2 (qC5H4), 72.2 (C5H3), 73.1 (d,
3
2JP, C= 3.6 Hz, C5H3), 73.2 (d, JP, C = 3.0 Hz, C5H4), 75.3 (C5H4), 75.8 (d,
1,1′-Bis(2-(E)-phenylvinyl)-2-(diphenylphosphino)ferrocene
(4h). Compound 4h was synthesized according to the general pro-
cedure using diethyl benzylphosphonate (1.17 g, 5.12 mmol) and
3h (0.36 g, 0.85 mmol). After evaporation of all volatiles in vacuo
4h was obtained as a dark orange solid.
JP, C = 1.2 Hz, C5H4), 75.9 (d, JP, C = 9.0 Hz, qC5H3), 76.9 (C5H4), 88.7
1
(d, JP, C = 21.0 Hz, qC5H3), 125.8 (d, JP, C = 12.0 Hz, CHCHPh), 126.5
2
3
3
(CHPh), 127.3 (CHPh), 127.9 (CHPh), 128.2 (PPh), 128.6 (d, JP, C
=
5.9 Hz, PPh), 128.7 (d, 3JP, C = 8.0 Hz, PPh), 129.0 (CHPh), 129.8 (PPh),
2
2
132.5 (d, JP, C = 17.4 Hz, PPh), 135.9 (d, JP, C = 21.4 Hz, PPh), 137.7
(d, JP, C = 8.4 Hz, qPPh), 138.3 (qCHPh), 140.4 (d, JP, C = Hz, qPPh).
31P{1H} NMR (CDCl3, δ): –23.3 (s). HRMS: m/z: calcd. for C39H45FePSi:
628.2378, found 628.2322 [M]+.
1
1
Yield 187 mg (0.33 mmol, 38 % based on 3h). Anal. calcd. for
C28H24Fe (416.34 g/mol): C, 79.45; H, 5.44; found C, 78.59; H, 5.63
3
(best match). Mp. 151 °C. 1H NMR (CDCl3, δ): 3.83 (ddd, JH,H
=
4
3
2.2 Hz, JH,H = 1.0 Hz, JH,P = 1.0 Hz, 1H, C5H3), 4.09–4.11 (m, 2H,
C5H4), 4.30 (ddd, JH,H = 2.4, 2.4 Hz, JH,H = 1.4 Hz, 1H, C5H4), 4.42
1′-tert-Butyldiphenylsilyl-1-(2-(E)-phenylvinyl)-2-(diphenyl-
phosphino)ferrocene (4f). Compound 4f was synthesized accord-
ing to the general procedure using diethyl benzylphosphonate
(0.10 g, 0.45 mmol) and 3f (0.10 g, 0.15 mmol). After evaporation
of all volatiles in vacuo 4f was obtained as a dark orange oil.
3
4
3
3
(dd, JH,H = 2.5, 2.5 Hz, 1H, C5H3), 4.48 (ddd, JH,H = 2.6, 2.6 Hz,
4JH,H = 1.4 Hz, 1H, C5H4), 4.81 (ddd, JH,H = 2.5 Hz, JH,H = 1.4 Hz,
3
4
4JH,P = 1.4 Hz, 1H, C5H3), 6.58 (d, JH,H = 16.4 Hz, 1H, ′CHPh), 6.61
3
(d, 3JH,H = 16.4 Hz, 1H, ′CHCHPh), 6.69 (d, 3JH,H = 16.1 Hz, 1H, CHPh),
3
4
Yield 75 mg (0.11 mmol, 71 % based on 3f). 1H NMR (CDCl3, δ): 7.08 (dd, JH,H = 16.1 Hz, JH,P = 2.4 Hz, 1H, CHCHPh), 7.13–7.27 (m,
1.01 (s, 9H, CH3), 3.54–3.57 (m, 1H, C5H3), 3.64–3.67 (m, 1H, C5H4),
15H, PPh, CHPh, ′CHPh), 7.41–7.46 (m, 3H, PPh), 7.61–7.67 (m, 2H,
3
3.87 (dd, 3JH,H = 2.5, 2.5 Hz, 1H, C5H3), 4.24–4.27 (m, 1H, C5H4), 4.27–
PPh). 13C{1H} NMR (CDCl3, δ): 68.1 (C5H4), 69.4 (d, JC,P = 3.0 Hz,
Eur. J. Inorg. Chem. 2020, 1–16
12
© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim