122.48 (s, OCH2CH CH2), 117.16 (s, OCH2CH CH2), 77.06 (s,
OCH2CH CH2), 76.93 (s, OCH2CH2CH3), 31.36, 31.18, 31.03 (3
exact assignment was not possible), 32.33 (s, C6H4CH(CH3)2),
31.56, 31.16 and 30.07 (3 s, ArCH2Ar), 23.27 (s, OCH2CH2CH3),
21.93 and 21.80 (s, C6H4CH(CH3)2), 17.52 (s, CH3C6H4), 10.37
1
s, ArCH2Ar), 23.35 (s, CH2CH3), 10.43 (s, CH3). 31P{ H} NMR
1
(120 MHz, CDCl3): d - 4.1 (s, PPh2). Found: C, 78.09; H, 6.47%.
Calc. for C64H62O4P2·2CH3OH (Mr = 957.12 + 64.08): C, 77.62;
H, 6.91.
(s, OCH2CH2CH3). 31P{ H} NMR (120 MHz, CDCl3): d 24.2 (s,
PPh2). Found: C, 55.48; H, 4.68%. Calc. for C84H90Cl2O4P2Ru2
(Mr = 1367.37): C, 73.78; H, 6.63.
(P,P)-Dichlorido-{5,11-bis(diphenylphosphino)-27,28-diallyloxy-
25,26 dipropoxycalix[4]arene} digold(I) (6)
Bis[(l2-5,11-bis(diphenylphosphanyl)-25,26-dipropoxy-27,28-
bis(allyloxy)calix[4]arene-P:P¢]disilver(I) bis(tetrafluoroborate) (8)
To a stirred solution of 5 (0.113 g, 0.120 mmol) in CH2Cl2 (10 mL)
was added a solution of [AuCl(tht)] (0.076 g, 0.236 mmol) in thf
(1 mL). After 2 h, the solution was concentrated to ca. 1 mL.
Addition of hexane afforded 6 as a white precipitate (0.120 g, 71%).
A three-necked flask containing CH2Cl2 (500 mL) was equipped
with 2 addition funnels respectively containing a solution of
AgBF4 (0.012 g, 0.062 mmol) in CH2Cl2/THF (250 : 1 mL), and a
solution of 5 (0.060 g, 0.062 mmol) in CH2Cl2 (250 mL). The latter
two solutions were added dropwise over 2 h into the flask under
vigorous stirring. After 12 h the solution was concentrated to ca.
5 mL. Addition of Et2O afforded 8 as a white precipitate (0.060 g,
84%). 1H NMR (CD2Cl2, 500 MHz, 25 ◦C): d 7.58–7.44 and 7.33–
7.24 (40H, PPh2), 7.21–7.08, 6.75–6.70, 6.69–6.61 (3 broad signals,
2H, arom. H of calix), 6.30 (ddt, 4H, OCH2CH CH2), 5.32–
5.24 (m, 8H, OCH2CH CH2), 4.60 and 4.54 (m, ABXYZ spin
system, 8H, OCH2CH CH2), 4.47 and 3.21 (AB spin system, 8H,
ArCH2Ar, 2J (AB) = 13.0 Hz), 4.44 and 3.12 (two overlapping AB
◦
1
Mp 240 C (dec.). H NMR (CDCl3): d 7.67–7.09 (20H, PPh2),
6.88–6.82, 6.67–6.61 and 6.49–6.44 (3 m, 10H, m-H of OArP and m
and p-H of OAr), 6.33–6.21 (ddt, 2H, OCH2CH CH2), 5.29–5.21
(4H, OCH2CH CH2), 4.61–4.38 (m, 4H, OCH2CH CH2), 4.48
2
and 3.24 (AB spin system, 2H, ArCH2Ar, J (AB) = 13.1 Hz),
4.44 and 3.15 (AB spin system, 4H, ArCH2Ar, 2J (AB) =
13.1 Hz), 4.39 and 2.99 (AB spin system, 2H, ArCH2Ar, 2J (AB) =
13.1 Hz), 3.96–3.79 (m, 4H, OCH2CH2CH3), 1.95 (pseudo sext,
4H, OCH2CH2CH3, 3J = 7.4 Hz), 1.00 (t, 6H, OCH2CH2CH3, 3J =
1
2
7.4 Hz). 13C{ H} NMR (CDCl3): d 158.81 and 156.36 (2 s, arom.
spin systems, 8H, ArCH2Ar, J (AB) = 12.5 Hz), 3.87 and 3.81
(ABX3 spin system, 8H, OCH2CH2CH3), 1.95 (pseudo sext, 8H,
Cq–O), 135.15–127.54 (arom. C’s), 122.95 (s, OCH2CH CH2),
118.42 (s, OCH2CH CH2), 77.53 (s, OCH2CH CH2), 76.29 (s,
OCH2CH2CH3), 31.47, 31.16, 30.93 (3 s, ArCH2Ar), 23.39 (s,
3
3
OCH2CH2CH3, J = 7.5 Hz), 1.01 (t, 12H, OCH2CH2CH3, J =
7.5 Hz). 13C{ H} NMR (CD2Cl2): d 157.11 and 156.78 (2 s, arom.
1
1
OCH2CH2CH3), 10.40 (s, OCH2CH2CH3). 31P{ H} NMR (120
Cq–O), 138.90–128.47 (arom. C’s), 122.76 (s, OCH2CH CH2),
117.41 (s, OCH2CH CH2), 77.39 and 76.40 (2 s, OCH2CH2CH3
OCH2CH CH2, exact assignment was not made), 31.02, 30.98
and 30.83 (3 s, ArCH2Ar), 23.45 (s, OCH2CH2CH3), 10.39 (s,
MHz, CDCl3): d 33.8 (s, PPh2). Found: C, 55.48; H, 4.68%. Calc.
for C64H62Au2Cl2O4P2·C6H14 (Mr = 1421.96 + 86.17): C, 55.75; H,
5.08. Slow diffusion of pentane into a dichloromethane solution of
the complex yielded colorless crystals suitable for X-ray diffraction
study.
◦
OCH2CH2CH3). 31P{ H} NMR (121 MHz, CDCl3, 25 C): d 11.2
(two d, PPh2, J(107Ag,P) = 435 Hz, J(109Ag,P) = 505 Hz). Found:
C, 66.80; H, 5.29%; calc. for C128H124Ag2B2F8O8P4 (Mr = 2303.59):
C, 66.74; H, 5.43. MS (ESI TOF): m/z (%) = 2165.6 (100) [M -
2BF4 + K]+ (expected isotopic profile).
1
Bis(g6-p-cymene)-tetrachlorido-P,P-[5,11-bis(diphenylphosphino)-
27,28-diallyloxy-25,26-dipropoxycalix[4]arene] diruthenium(II) (7)
A solution of [RuCl2(p-cymene)]2 (0.067 g, 0.110 mmol) in CH2Cl2
(10 mL) was added to a solution of 5 (0.105 g, 0.11 mmol)
in CH2Cl2 (20 mL). After stirring overnight, the solution was
evaporated to dryness and the residue was taken-up with CHCl3.
Addition of Et2O afforded 7 as an orange precipitate (0.120 g,
Bis(g5-cyclopentadienyl)-bis[l2-5,11-bis(diphenylphosphino)-
27,28-diallyloxy-25,26-dipropoxycalix[4]arene] nickel(II)
bis(tetrafluoroborate) (9)
A three-necked flask containing CH2Cl2 (500 mL) was equipped
with two addition funnels containing a solution of [Ni(h -
◦
1
5
70%). Mp 220 C. H NMR (CDCl3): d 7.61–7.19 (24H, PPh2
and m-H of OArP), 6.93–6.90, 6.83–6.77 and 6.55–6.50 (3 m, 6H,
m and p-H of OAr), 6.36–6.23 (ddt, 2H, OCH2CH CH2), 5.20,
4.97, 4.86 and 4.75 (ABCD spin system, 4H, C6H4CH3, 3J(AB) =
4.2 Hz, 3J(CD) = 5.4 Hz), 5.19–5.16 (4H, OCH2CH CH2), 4.57–
4.46 (m, 4H, OCH2CH CH2), 4.54 and 3.27 (AB spin system,
2H, ArCH2Ar, 2J (AB) = 13.2 Hz), 4.48 and 3.24 (AB spin
C5H5)(cod)]BF4 (0.018 g, 0.056 mmol) in CH2Cl2 (250 mL) and a
solution of 5 (0.054 g, 0.056 mmol) in CH2Cl2 (250 mL), respec-
tively. These solutions were added dropwise and simultaneously
over 2 h into the flask under vigorous stirring. After 12h, the
solution was concentrated to ca. 5 mL. Addition of Et2O afforded
1
9 as a yellow precipitate (0.055 g, 85%). H NMR (CDCl3, 500
system, 4H, ArCH2Ar, J (AB) = 13.1 Hz), 4.33 and 2.98 (AB
MHz, 25 ◦C): d 7.73–5.57 (60H, arom. H), 6.48 (br signal, 4H,
OCH2CH CH2), 5.31–5.16 (m, 26H, C5H5, OCH2CH CH2,
and OCH2CH CH2), 5.25 (m, 2H, OCH2CH CH2), 4.62 and
2
spin system, 2H, ArCH2Ar, 2J (AB) = 13.1 Hz), 4.01–3.85 (m, 4H,
OCH2CH2CH3), 2.76 (quint., 2H, C6H4CH(CH3)2, 3J = 6.9 Hz),
1.96 (pseudo sext, 4H, OCH2CH2CH3, 3J = 7.5 Hz), 1.58 (s, 3H,
CH3C6H4), 1.07 (d, 6H, C6H4CH(CH3)2, 3J = 7.5 Hz), 1.05 (d, 6H,
2
3.55 (AB spin system, 4H, ArCH2Ar, J (AB) = 13.2 Hz), 4.53
2
and 3.31 (AB spin system, 4H, ArCH2Ar, J (AB) = 13.2 Hz),
3
3
C6H4CH(CH3)2, J = 7.5 Hz), 1.00 (t, 6H, OCH2CH2CH3, J =
4.51 and 3.20 (AB spin system, 4H, ArCH2Ar, 2J (AB) = 13.2 Hz),
4.50 and 3.17 (AB spin system, 4H, ArCH2Ar, 2J (AB) = 13.2 Hz),
4.12 (m, 4H, OCH2CH2CH3), 3.87 (m, 4H, OCH2CH2CH3), 1.99
(br signal, 8H, OCH2CH2CH3), 1.11 (t, 6H, OCH2CH2CH3, 3J =
7.4 Hz). 13C{ H} NMR (CDCl3): d 157.75 and 156.47 (2 s, arom.
1
Cq–O), 136.15–127.55 (arom. C’s), 122.70 (s, OCH2CH CH2),
117.95 (s, OCH2CH CH2), 110.40 and 95.52 (2 s arom. Cq of
C6H4), 77.25, 77.16 (2 s, OCH2CH2CH3 and OCH2CH CH2,
1
7.4 Hz), 0.95 (t, 6H, OCH2CH2CH3, 3J = 7.4 Hz). 31P{ H} NMR
10068 | Dalton Trans., 2011, 40, 10063–10070
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