concentrated under vacuum. Addition of MeOH and cooling
to Ϫ78 ЊC afforded 12 as a pale yellow solid. Yield: 0.163 g,
0.156 mmol, 68%. Mp > 240 ЊC. IR (CH2Cl2) νmax/cmϪ1: 1755
(C᎐O). 1H NMR (300 MHz, CDCl ): δ 9.64–9.60 (m, 1H, arom.
Chloro(ꢁ3-2-methylallyl){5,11,17,23-tetra-tert-butyl-25-
(ethoxycarbonylmethoxy)-26,27,28-(ꢀ3-phosphorustrioxy)-
calix[4]arene}palladium(II) (15). L2 (0.186 g, 0.244 mmol) was
added to a solution of [Pd(η3-C4H7)Cl]2 (0.048 g, 0.12 mmol)
in CH2Cl2 (10 cm3). After stirring for 15 h, the solution was
concentrated to ca. 50%. Addition of hexane and cooling to
Ϫ78 ЊC gave 15 as a white powder. Yield: 0.160 g, 0.167 mmol,
᎐
3
H of 8-mq), 8.28 (d, 3J = 7.1, 1H, arom. H of 8-mq), 7.61–7.44
(m, 4H, arom. H of 8-mq), 7.21–7.05 (m, 6H, m-ArH), 6.77 (s,
2
2H, m-ArH), 5.07 and 3.54 (AB q, J = 13.9, 4H, ArCH2Ar),
2
4.71 and 3.49 (AB q, J = 14.0, 4H, ArCH2Ar), 4.71 (s, 2H,
68%. Mp > 240 ЊC. IR (nujol) νmax/cmϪ1: 1734 (C᎐O). 1H NMR
᎐
OCH2CO2), 3.84 (s, 2H, CH2 of 8-mq), 3.66 (q, 3J = 7.2 Hz, 2H,
CH2CH3), 1.36 [s, 18H, C(CH3)3], 1.22 [s, 9H, C(CH3)3], 0.96
(400 MHz, CDCl3): δ 7.22–7.19 and 7.11–7.10 (2 overlapping
AB q, 4H, m-ArH), 7.07 (s, 2H, m-ArH), 6.73 and 6.71 (AB q,
3
2
[s, 9H, C(CH3)3], 0.88 (t, J = 7.1 Hz, 3H, CH2CH3); 13C{1H}
2H, m-ArH), 5.01 and 3.54 (AB q, J = 14.4, 2H, ArCH2Ar),
2
NMR (50 MHz, CDCl3): δ 169.77 (s, CO), 153.25–121.19
(aryl C), 71.62 (s, OCH2CO2), 60.25 (s, CH2CH3), 36.12 (s,
ArCH2Ar), 34.42 [s, C(CH3)3], 34.12 [s, ArCH2Ar and
C(CH3)3], 33.93 [s × 2, C(CH3)3], 31.40 [s × 3, C(CH3)3], 31.11
[s, C(CH3)3], 13.80 (s, CH2CH3), the CH2 signal of 8-mq was
not detected. 31P{1H} NMR (121 MHz, CDCl3): δ 88.7 [s,
P(OAr)3]. Found: C, 66.80; H, 6.43; N, 1.42; calc. for
C58H67ClNO6PPd (Mr = 1047.00): C, 66.53; H, 6.45; N, 1.34%.
5.00 and 4.72 (AB q, J = 16.4, 2H, OCH2CO2), 4.93 and 3.56
(AB q, 2J = 15.0, 2H, ArCH2Ar), 4.45 and 3.46 (AB q, 2J = 13.6,
2H, ArCH2Ar), 4.43 (br s, 1H, H-allyl), 4.41 and 3.49 (AB q,
2J = 13.2, 2H, ArCH2Ar), 4.14 (q, 3J = 7.2, 2H, OCH2CH3), 3.47
(br s, 1H, H-allyl), 3.16 (br s, 1H, H-allyl), 2.55 (br s, 1H,
H-allyl), 1.85 (s, 3H, CH3-allyl), 1.37 [s, 9H, C(CH3)3], 1.36 [s,
3
9H, C(CH3)3], 1.25 (t, J = 7.2 Hz, OCH2CH3), 1.18 [s, 9H,
C(CH3)3], 0.90 [s, 9H, C(CH3)3]; 13C{1H} NMR (50 MHz,
CDCl3): δ 170.73 (s, CO2), 153.77–124.60 (aryl C and Cquat
-
Chloro(8-methylquinolinylmethyl-C,N){5,11,17,23-tetra-tert-
butyl-25-(diethylcarbamoylmethoxy)-26,27,28-(ꢀ3-phosphorus-
trioxy)calix[4]arene}palladium(II) (13). L3 (0.175 g, 0.22 mmol)
was added to a solution of [Pd(8-mq)Cl]2 (0.063 g, 0.111 mmol)
in CH2Cl2 (20 cm3). After stirring for 24 h, the solution was
concentrated under vacuum. Addition of hexane and cooling to
Ϫ78 ЊC afforded 13 as a pale yellow solid. Yield: 0.170 g, 0.158
allyl), 78.62 and 77.54 (s × 2, CH2-allyl), 71.95 (s, OCH2CO2),
60.73 (s, OCH2CH3), 36.31 and 35.99 (s × 2, ArCH2Ar), 34.45
[s × 2, C(CH3)3], 34.18 [s × 2, C(CH3)3], 33.98 (s × 2,
ArCH2Ar), 31.49 [s × 3, C(CH3)3], 31.11 [s, C(CH3)3], 23.27 (s,
CH3-allyl), 14.24 (s, OCH2CH3); 31P{1H} NMR (121 MHz,
CDCl3): δ 107.0 [s, P(OAr)3]. Found: C, 67.23; H, 7.10; calc. for
C52H66ClO6PPd (Mr = 959.92): C, 67.06; H, 6.93%.
mmol, 71%. Mp > 233 ЊC (decomp.). IR (CH2Cl2) νmax/cmϪ1
:
1655 (C᎐O). 1H NMR (300 MHz, CDCl ): δ 9.66–9.62 (m, 1H,
Acetylacetonatocarbonyl{5,11,17,23-tetra-tert-butyl-25-(di-
᎐
3
arom. H of 8-mq), 8.29–8.26 (m, 1H, arom. H of 8-mq), 7.61–
7.44 (m, 4H, arom. H of 8-mq), 7.20 (br s, 2H, m-ArH), 7.12
(s, 2H, m-ArH), 7.10 (s, 2H, m-ArH), 6.75 (s, 2H, m-ArH), 5.10
phenylphosphinoylmethoxy)-26,27,28-(ꢀ3-phosphorustrioxy)-
calix[4]arene}rhodium(I) (16). L1 (0.134 g, 0.15 mmol) was
added‡ to a solution of [Rh(acac)(CO)2] [acac = MeC(O)-
CHC(O)Me] (0.040 g, 0.151 mmol) in CH2Cl2 (30 cm3). After
stirring for 12 h, the volatiles were evaporated under vacuum to
give 16 as a yellow powder. Owing to its high solubility in all
common organic solvents, 16 was not purified further. Yield:
2
and 3.56 (AB q, J = 13.9, 4H, ArCH2Ar), 4.79 (s, 2H, OCH2-
CON), 4.70 and 3.49 (AB q, 2J = 14.0, 4H, ArCH2Ar), 3.82 (s,
3
3
2H, CH2Pd), 3.07 (q, J = 7.1, 2H, CH2CH3), 2.87 (q, J = 7.1
Hz, 2H, CH2CH3), 1.36 [s, 18H, C(CH3)3], 1.21 [s, 9H,
C(CH3)3], 0.95 [s, 9H, C(CH3)3], 0.67 (t, 3J = 7.1 Hz, 3H,
0.156 g, 0.139 mmol, 92%. Mp 76–78 ЊC. IR (CH2
Cl ) ν
/
2
max
cmϪ1: 2004s (CO), 1182 (s, P᎐O, tentative assignment). 1H
3
CH2CH3), 0.48 (t, J = 7.1 Hz, 3H, CH2CH3). 13C{1H} NMR
᎐
NMR (300 MHz, CDCl3): δ 8.00–7.93 and 7.53–7.44 [10 H,
P(O)Ph2], 7.05 (s, 4H, m-ArH), 7.02 (s, 2H, m-ArH), 6.35 (s, 2H,
m-ArH), 5.37 (s, 1H, CH-acac), 4.79 [d, 2J = 4.4, 2H, P(O)CH2],
(50 MHz, CDCl3): δ 167.64 (s, CO), 153.71–121.19 (aryl C),
72.86 (s, OCH2), 41.35 and 39.89 (s × 2, CH2CH3), 36.16 (s,
ArCH2Ar), 34.45 [s, C(CH3)3], 34.31 (s, ArCH2Ar), 34.10 [s ×
2, C(CH3)3], 33.93 [s, C(CH3)3], 31.48 [s × 3, C(CH3)3], 31.15
[s, C(CH3)3], 27.12 (s, CH2 of 8-mq), 13.77 and 12.61 (s × 2,
CH2CH3); 31P{1H} NMR (121 MHz, CDCl3): δ 88.1 [s,
P(OAr)3]. Found: C, 67.14; H, 6.60; N, 2.48; calc. for C60H72-
ClN2O5PPd (Mr = 1074.07): C, 67.09; H, 6.79; N, 2.61%.
2
4.52 and 3.40 [AB q, J = 14.6, 4H, ArCH2Ar], 4.52 and 3.29
2
[AB q, J = 14.9 Hz, 4H, ArCH2Ar], 1.99 (s, 3H, CH3-acac),
1.36 (s, 3H, CH3-acac), 1.33 [s, 18H, C(CH3)3], 1.17 [s, 9H,
C(CH3)3], 0.70 [s, 9H, C(CH3)3]. 13C{1H} NMR (75 MHz,
CDCl3): δ 187.23 and 187.00 (s × 2, CO), 146.29–124.13 (aryl
C), 101.65 (s, CH-acac), 73.21 [d, J(PC) = 56 Hz, P(O)CH2],
35.83 and 35.34 (s × 2, ArCH2Ar), 34.08 [s × 2, C(CH3)3], 33.63
Chloro(o-dimethylaminomethylphenyl-C,N){5,11,17,23-tetra-
tert-butyl-25-(diphenylphosphinoylmethoxy)-26,27,28-(ꢀ3-phos-
phorustrioxy)calix[4]arene}palladium(II) (14). L1 (0.107 g,
0.12 mmol) was added to a solution of [Pd(o-C6H4CH2-
NMe2)Cl]2 (0.031 g, 0.06 mmol) in CH2Cl2 (10 cm3). After
stirring for 1 h, the solvent was removed under vacuum. Re-
crystallisation from CH2Cl2–hexane at Ϫ78 ЊC gave 14 as a pale
yellow solid. Yield: 0.072 g, 0.062 mmol, 52%. Mp > 186 ЊC
[s × 2, C(CH3
) ], 33.11 (s × 2, ArCH Ar), 31.42 [s × 3,
3
2
C(CH3)3], 31.33 [s, C(CH3)3], 26.94 (CH3-acac), 25.46 (CH3-
acac). 31P{1H} NMR (121 MHz, CDCl3): δ 104.0 [d, J(PRh) =
300 Hz, P(OAr)3], 28.0 [s, P(O)Ph2]. Found: C, 67.66; H, 6.53;
calc. for C63H71O8P2Rh (Mr = 1121.09): C, 67.49; H, 6.38%.
Acetylacetonatocarbonyl{5,11,17,23-tetra-tert-butyl-25-
(ethoxycarbonylmethoxy)-26,27,28-(ꢀ3-phosphorustrioxy)calix-
[4]arene}rhodium(I) (17). L2 (0.111 g, 0.15 mmol) was added
to a solution of [Rh(acac)(CO)2] (0.040 g, 0.15 mmol) in
CH2Cl2 (30 cm3). After stirring for 12 h, the volatiles were
evaporated under vacuum to give 17 as a yellow powder. Yield:
(decomp). IR (KBr) νmax/cmϪ1: 1185 (P᎐O, tentative assign-
᎐
ment). 1H NMR (200 MHz, CDCl3): δ 7.64–7.38, 7.28–7.19 and
7.06–6.62 (20 H, arom. H), 6.41 (s, 2H, m-ArH of calix), 5.17 (s,
2H, P(O)CH2), 4.77–4.70 (m, 4H, ArCH2Ar), 3.93 (s, 2H,
2
2
NCH2), 3.44 (d, J = 14, 2H, ArCH2Ar), 3.01 (d, J = 14, 2H,
4
0.135 g, 0.136 mmol, 90%. Mp 109–111 ЊC. IR (CH2Cl2) νmax
/
ArCH2Ar), 2.76 [d, J(PH) = 4.2 Hz, 6H, N(CH3)2], 1.31 [s,
1
cmϪ1: 2001s (CO), 1755m (C᎐O ester). H NMR (200 MHz,
18H, C(CH3)3], 1.19 [s, 9H, C(CH3)3], 0.86 [s, 9H, C(CH3)3].
᎐
2
13C{1H} NMR (50 MHz, CDCl3): δ 153.90–122.60 (aryl C),
CDCl3): δ 7.18 and 7.07 (AB q, J = 2.4, 4H, m-ArH), 7.05
3
(s, 2H, m-ArH), 6.59 (s, 2H, m-ArH), 5.36 (s, 1H, CH-acac),
72.90 [d, J(PC) = 4.9 Hz, NCH2], 72.65 [d, J(PC) = 80.8 Hz,
2
4.98 and 3.57 (AB q, J = 14.6, 4H, ArCH2Ar), 4.64 (s, 2H,
P(O)CH2], 50.38 [s × 2, N(CH3)2], 36.16 (s × 2, ArCH2Ar),
34.32 [s, C(CH3)3], 33.93 [s, C(CH3)3], 33.67 (s × 2, ArCH2Ar),
31.34 [s × 3, C(CH3)3], 31.01 [s, C(CH3)3]. 31P{1H} NMR (121
MHz, CDCl3): δ 82.3 [s, P(OAr)3], 26.5 [s, P(O)Ph2]. Found:
C, 68.10; H, 6.86; N, 1.24; calc. for C66H76ClNO5P2Pd (Mr =
1167.13): C, 67.92; H, 6.56; N, 1.20%.
OCH2CO2), 4.58 and 3.43 (AB q, 2J = 14.6, 4H, ArCH2Ar), 4.19
3
(q, J = 7.1, OCH2CH3), 2.03 (s, 3H, CH3-acac), 1.45 (s, 3H,
‡ L1 needs to be free of NEt3HCl. The presence of the latter leads to
formation of complex 19.
4272
J. Chem. Soc., Dalton Trans., 2002, 4264–4274