Organometallics
Article
[t, 1H, 8.0 Hz, H-4], 7.20 [t, 1H, 8.0 Hz, H-5], 4.47 [t, 2H, 1.8 Hz, H-
2′ and H-5′], 4.24 [t, 2H, 1.8 Hz, H-3′ and H-4′], 4.03 [s, 5H, H-6′ to
H-10′] ppm. 13C NMR (CDCl3): δC 174.8 [COO], 139.3 [C-2],
131.7 [C-4], 130.9 [C-6], 129.3 [C-3], 128.3 [C-1], 125.8 [C-5], 85.5
[C-1′], 69.7 [C-6′ to C-10′], 69.6, 68.5 [C-2′ to C-5′] ppm.
3-Ferrocenylbenzoic Acid (FcL2H). The preparation and workup of
FcL2H was carried out in the same manner as that described for
FcL1H except that anthranilic acid was replaced by 3-aminobenzoic
acid. The product was crystallized from a methylene dichloride and
hexane (1/3) mixture, giving orange crystals. Mp: 165−167 °C. Yield:
50%. IR (cm−1): 1686 ν(OCO)asym, 1606, 1432, 1412, 1299, 1267,
1192, 1106, 999, 814, 759, 698, 560, 493, 479. Electronic absorption
data (λmax, nm (ε, M−1 cm−1)): DMSO, 292 (22800), 351sh (5800),
458sh (1600); chloroform, 285 (21300), 352sh (3100), 458sh (900).
Emission data in DMSO (λem, nm; ϕf): 413 at λex 300 nm; 0.005. 1H
NMR (CDCl3): δH 13.6 [br, 1H, COOH], 8.14 [s, 1H, H-2], 7.87 [d,
1H, 8.0 Hz, H-6], 7.64 [d, 8.0 Hz, H-4], 7.32 [t, 1H, 8.0 Hz, H-5],
4.64 [t, 2H, 1.8 Hz, H-2′ and H-5′], 4.29 [t, 2H, 1.8 Hz, H-3′ and H-
4′], 3.98 [s, 5H, H-6′ to H-10′] ppm. 13C NMR (CDCl3): δC 172.5
[COO], 140.2 [C-1], 131.2 [C-5], 129.4 [C-3], 128.5 [C-4], 127.5
[C-6], 127.4 [C-2], 83.8 [C-1′], 69.7 [C-6′ to C-10′], 69.3, 66.6 [C-
2′ to C-5′] ppm. 1H NMR data reported for the product obtained by
hydrolysis of 3-ferrocene ethylbenzoate75 correspond to the data
obtained for FcL2H; however there is no mention of melting point
and other spectroscopic data.
Synthesis and Characterization of Ferrocene-Appended
Triorganotin(IV) Compounds. A general method was followed for
the synthesis of ferrocene-appended triphenyltin compounds 1, 3, and
9. In a typical procedure, a mixture of Ph3SnOH and the appropriate
metallo pro-ligands FcLnH (n = 1−3) in a 1:1 stoichiometric ratio was
heated to reflux in anhydrous toluene (50 mL) for 8 h in a round-
bottom flask equipped with a Dean−Stark apparatus and a water-
cooled condenser. The reaction mixture was filtered while hot, and
the solvent was removed using a rotary evaporator. The residue was
washed, boiled with hexane, filtered, and dried in vacuo. The residue
was recrystallized using appropriate solvent(s) to yield the desired
product. An analogous procedure was followed for the synthesis of the
tributyltin(IV) compounds 2, 4 and 8, but using (Bu3Sn)2O and
FcLnH in a 1:2 stoichiometric ratio. The triorganotin(IV) compounds
5−7 and 10 were prepared by metathesis of the appropriate R3SnCl
starting material (R = Me, Et, Pr, Cy) with FcL3H in equimolar
proportions in anhydrous methanol using reflux conditions. The
specific details pertaining to reactants and analytical and character-
ization data for the complexes are given below.
(15100), 348sh (2300), 448sh (600). Emission data in DMSO (λem,
nm; ϕf): 406 at λex 300 nm; 0.034. H NMR (CDCl3): δH 7.72 [d,
1
1H, 8.0 Hz, H-6], 7.43 [d, 1H, 8.0 Hz, H-3], 7.29 [t, 1H, 8.0 Hz, H-
4], 7.13 [t, 1H, 8.0 Hz, H-5], 4.39 [t, 2H, 1.8 Hz, H-2′ and H-5′],
4.16 [t, 2H, 1.8 Hz, H-3′ and H-4′], 4.00 [s, 5H, H-6′ to H-10′], Sn-
Bu moiety: 1.47−1.55 [m, 6H, H-1*], 1.17−1.27 [m, 12H, H-2* and
H-3*], 0.82 [t, 9H, H-4*] ppm. 13C NMR (CDCl3): δC 174.7
[COO], 137.6 [C-2], 134.3 [C-1], 131.2 [C-4], 129.2 [C-6], 128.3
[C-3], 125.8 [C-5], 86.9 [C-1′], 69.5 [C-6′ to C-10′], 69.4, 68.0 [C-
2′ to C-5′], Sn-Bu moiety: (nJ(13C−119Sn, Hz)): 27.8 [(20), C-2*],
27.0 [(65), C-3*], 16.4 [(355), C-1*], 13.6 [(nd), C-4*] ppm. 119Sn
NMR (CDCl3): δSn 115.5 ppm.
[FcL2SnPh3] (3). Recrystallized from an acetonitrile and hexane (1/
1) mixture to give an orange microcrystalline product in 71% yield.
Mp: 159−160 °C. Anal. Calcd for C35H28FeO2Sn: C, 64.15; H, 4.31.
Found: C, 64.44; H, 4.10. IR (cm−1): 1634 ν(OCO)asym, 1608, 1563,
1480, 1430, 1418, 1331, 1300, 1283, 1261, 1179, 1129, 1104, 1075,
997, 888, 817, 782, 729, 696, 660, 591, 525, 501, 481. Electronic
absorption data (λmax, nm (ε, M−1 cm−1)): DMSO, 290 (22700),
353sh (4200), 447sh (1500); chloroform, 285 (20500), 348sh
(3000), 447sh (800). Emission data in DMSO (λem, nm; ϕf): 409 at
λex 300 nm; 0.011. 1H NMR (CDCl3): δH 8.14 [s, 1H, H-2], 7.91 [d,
1H, 8.0 Hz, H-6], 7.60−7.80 [m, 6H, H-2*], 7.35−7.50 [m, 9H, H-3*
and H-4*], 7.25−7.35 [m, 2H, H-4 and H-5], 4.63 [t, 2H, 1.8 Hz, H-
2′ and H-5′], 4.26 [t, 2H, 1.8 Hz, H-3′ and H-4′], 3.96 [s, 5H, H-6′ to
H-10′] ppm. 13C NMR (CDCl3): δC 174.0 [COO], 139.1 [C-1],
138.1 [1J(13C−119Sn) = nd, C-1*], 136.9 [2J(13C−119Sn) = 48 Hz, C-
2*], 131.6 [C-5], 130.4 [C-3], 130.1 [4J(13C-119/117Sn) = 13 Hz, C-
4*], 128.8 [3J(13C-119/117Sn) = 63 Hz, C-3*], 128.5 [C-4], 127.6 [C-
6], 126.8 [C-2], 84.2 [C-1′], 69.7 [C-6′ to C-10′], 69.3, 66.4 [C-2′ to
C-5′] ppm. 119Sn NMR (CDCl3): δSn −109.3 ppm.
[FcL2SnBu3] (4). Recrystallized from methanol to give an orange-
red powder in 73% yield. Mp: 74−76 °C. Anal. Calcd for
C29H40FeO2Sn: C, 58.52; H, 6.77. Found: C, 58.16; H, 6.80. IR
(cm−1): 1602 ν(OCO)asym, 1564, 1522, 1479, 1435, 1404, 1366,
1308, 1253, 1144, 1103, 1077, 948, 868, 815, 769, 680, 658, 608, 574,
511. Electronic absorption data (λmax, nm (ε, M−1 cm−1)): DMSO,
295 (20080), 356sh (3900), 454sh (1200); chloroform, 294 (21700),
360sh (4000), 452sh (1200). Emission data in DMSO (λem, nm; ϕf):
1
404 at λex 300 nm; 0.012. H NMR (CDCl3): δH 8.10 [s, 1H, H-2],
7.82 [d, 1H, 8.0 Hz, H-6], 7.53 [d, 8.0 Hz, H-4], 7.24 [t, 1H, 8.0 Hz,
H-5], 4.60 [t, 2H, 1.8 Hz, H-2′ and H-5′], 4.21 [t, 2H, 1.8 Hz, H-3′
and H-4′], 3.92 [s, 5H, H-6′ to H-10′]; Sn-Bu moiety, 1.45−1.64 [m,
6H, H-1*], 1.10−1.40 [m, 12H, H-2* and H-3*], 0.82 [t, 9H, H-4*]
ppm. 13C NMR (CDCl3): δC 174.7 [COO], 137.6 [C-1], 131.2 [C-
5], 129.1 [C-3], 128.3 [C-4], 125.8 [C-6 and C-2], 86.8 [C-1′], 69.5
[C-6′ to C-10′], 69.3, 67.9 [C-2′ to C-5′]; Sn-Bu moiety
(nJ(13C−119Sn, Hz)) 27.7 [(20), C-2*], 27.0 [(66), C-3*],16.4
[(356), C-1*], 13.6 [(nd), C-4*], ppm. 119Sn NMR (CDCl3): δSn
114.3 ppm.
[FcL1SnPh3] (1). Recrystallized from benzene to give an orange
microcrystalline product in 65% yield. Mp: 138−140 °C. Anal. Calcd
for C35H28FeO2Sn: C, 64.15; H, 4.31. Found: C, 63.97; H, 4.60. IR
(cm−1): 1638 ν(OCO)asym, 1618, 1598, 1528, 1430, 1417, 1367,
1249, 1169, 1143, 1120, 1023, 887, 833, 762, 733, 699, 654, 692, 562,
508, 478. Electronic absorption data (λmax, nm (ε, M−1 cm−1)):
DMSO, 286 (22500), 351sh (4200), 450sh (1300); chloroform, 294
[FcL3SnMe3(MeOH)]·MeOH (5). Recrystallized from methanol to
give an orange crystalline material in 72% yield. Mp: 162−164 °C.
Anal. Calcd for C22H30FeO4Sn: C, 49.55; H, 5.67. Found: C, 49.86;
H, 5.88. IR (cm−1): 1606 ν(OCO)asym, 1595, 1556, 1454, 1412, 1377,
1352, 1284, 1177, 1137, 1107, 1080, 1105, 889, 843, 786, 719, 709,
652, 550, 512, 480, 469. Electronic absorption data (λmax, nm (ε, M−1
cm−1)): DMSO, 295 (23100), 353sh (5000), 453sh (1600);
chloroform, 296 (11800), 365sh (1300), 465sh (500). Emission
(17500), 359sh (2900), 454sh (1000). Emission data in DMSO (λem
,
1
nm; ϕf): 413 at λex 300 nm; 0.025. H NMR (CDCl3): δH 8.13 [d,
1H, 8.0 Hz, H-6], 7.90 [d, 1H, 8.0 Hz, H-3], 7.65−7.84 [m, 6H, H-
2*], 7.50−7.65 [m, 2H, H-4 and H-5], 7.15−7.50 [m, 9H, H-3* and
H-4*], 4.62 [t, 2H, 1.8 Hz, H-2′ and H-5′], 4.25 [t, 2H, 1.8 Hz, H-3′
and H-4′], 3.96 [s, 5H, H-6′ to H-10′] ppm. 13C NMR (CDCl3): δC
174.0 [COO], 141.0 [C-2], 138.1 [1J(13C−119Sn) = 640 Hz, C-1*],
136.8 [2J(13C−119Sn) = 47 Hz, C-2*], 131.5 [C-4], 130.1
[4J(13C−119Sn) = 13 Hz, C-4*], 129.2 [C-6], 128.8 [3J(13C−119Sn)
= 63 Hz, C-3*], 128.5 [C-3], 128.4 [C-1], 125.0 [C-5], 84.2 [C-1′],
69.6 [C-6′ to C-10′], 69.2, 66.5 [C-2′ to C-5′] ppm. 119Sn NMR
(CDCl3): δSn −109.1 ppm.
1
data in DMSO (λem, nm; ϕf): 399 at λex 300 nm; 0.015. H NMR
(CDCl3): δH 7.89 [d, 2H, 8.0 Hz, H-2 and H-6], 7.41 [d, 2H, 8.0 Hz,
H-3 and H-5], 4.62 [t, 2H, 1.8 Hz, H-2′ and H-5′], 4.28 [t, 2H, 1.8
Hz, H-3′ and H-4′], 3.93 [s, 5H, H-6′ to H-10′], 3.41 [s, 3H,
2
MeOH]; Sn-Me moiety, 0.56 [s, 3H, J(1H−119Sn) = 56 Hz, H-1*]
[FcL1SnBu3]n (2). Recrystallized from toluene to give orange-red
microcrystalline product in 75% yield. Mp: 112−114 °C. Anal. Calcd
for C29H40FeO2Sn: C, 58.52; H, 6.77. Found: C, 58.86; H, 6.88. IR
(cm−1): 1602 ν(OCO)asym, 1580, 1557, 1462, 1396, 1386, 1288,
1261, 1152, 1106, 1023, 1003, 846, 812, 752, 694, 671, 650, 614, 589,
531, 511, 479. Electronic absorption data (λmax, nm (ε, M−1 cm−1)):
DMSO, 285 (21400), 350sh (4700), 440sh (1300); chloroform, 280
ppm. 13C NMR (CDCl3): δC 171.7 [COO], 144.1 [C-1], 130.2 [C-3
and C-5], 128.9 [C-4], 125.4 [C-2 and C-6], 83.6 [C-1′], 69.7 [C-6′
to C-10′], 69.5, 66.7 [C-2′ to C-5′], 51.4 [MeOH]; Sn-Me moiety −
2.28 [1J(13C−119Sn) = 394 Hz, C-1*] ppm. 119Sn NMR (CDCl3): δSn
136.6 ppm.
[FcL3SnEt3(MeOH)] (6). Recrystallized from methanol to give an
orange crystalline material in 68% yield. Mp: 92−94 °C. Anal. Calcd
N
Organometallics XXXX, XXX, XXX−XXX