Intramolecularly Coordinated Organolead(II) Compounds
CH3), 4.02Ϫ4.23 (complex pattern, 6 H, CH2), 4.28Ϫ4.40 (complex NMR (400.13 MHz, C6D6): δ ϭ Ϫ0.60 [s, 1 H, CH(SiMe3)2], 0.39
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pattern, 2 H, CH2), 6.86 (t, 1 H, aromatics), 7.04 (t, 2 H, aro-
matics), 7.33 (d, 2 H, aromatics), 8.05 (complex pattern, 2 H, aro-
(s, 18 H, SiMe3), 0.95 (t, 6 H, CH3), 1.16 (s, 9 H, CH3), 1.20 (t, 6 H,
CH3), 3.66Ϫ3.76 (complex pattern, 2 H, CH2), 3.83Ϫ3.93 (complex
pattern, 2 H, CH2), 4.07Ϫ4.24 (complex pattern, 4 H, CH2), 8.10
matics) ppm. 13C{1H} NMR (100.61 MHz, [D8]thf): δ ϭ 17.7 (d,
3
3JC,P ϭ 6 Hz, 2 C, CH3), 17.8 (d, JC,P ϭ 6 Hz, 2 C, CH3), 32.4 (s, (complex pattern,
2
H, aromatics) ppm. 13C{1H} NMR
2
3 C, CH3), 36.6 (s, 1 C, C), 63.9 (d, JC,P ϭ 6 Hz, 2 C, CH2), 65.0 (100.61 MHz, C6D6): δ ϭ 5.4 (s, 6 C, SiMe3), 16.3 (complex pat-
2
(d, JC,P ϭ 4 Hz, 2 C, CH2), 124.8 (s, 2 C, Cp), 129.2 (s, 2 C, Cm), tern, 2 C, CH3), 16.5 (complex pattern, 2 C, CH3), 31.1 (s, 3 C,
135.2 (s, 2 C, Co), 136.9 (dd, 2JC,P ϭ 17, 4JC,P ϭ 4 Hz, 2 C, C-3,5),
CH3), 34.7 (s, 1 C, C), 62.3 (complex pattern, CH2), 62.9 [s, 1 C,
1
3
2
4
137.2 (dd, JC,P ϭ 195, JC,P ϭ 25 Hz, 2 C, C-2,6), 145.3 (s, 1 C, C(H)(SiMe3)2], 134.4 (dd, JC,P ϭ 17, JC,P ϭ 5 Hz, 2 C, C-3,5),
3
2
Ci), 151.4 (t, JC,P ϭ 13 Hz, 1 C, C-4), 239.4 (t, JC,P ϭ 35 Hz, 1 135.8 (dd, 1JC,P ϭ 198, 3JC,P ϭ 25 Hz, 2 C, C-2,6), 149.0 (t, 3JC,P ϭ
C, C-1) ppm. 31P{1H} NMR (161.98 MHz, [D8]thf): δ ϭ 47.8 (s,
JP,Pb ϭ 123 Hz) ppm. 31P{1H} MAS NMR (161.98 MHz): δ ϭ
13 Hz, 1 C, C-4), 231.8 (t, JC,P ϭ 37 Hz, 1 C, C-1) ppm. 31P{1H}
2
NMR (161.98 MHz, C6D6): δ ϭ 42.1 (s, JP,Pb ϭ 125 Hz) ppm.
45.5, 50.4 ppm. IR (KBr): ν˜(PϭO) ϭ 1208, 1183 cmϪ1. UV/Vis 207Pb{1H} NMR (83.72 MHz, C6D6): δ ϭ 6874 (t, JP,Pb ϭ 129 Hz)
(CH3CN): λ ϭ 215 nm, ε ϭ 28695 L·molϪ1·cmϪ1; λ ϭ 259 nm, ε ϭ ppm. IR (KBr): ν˜(PϭO) ϭ 1208 cmϪ1. MS: m/z (%) ϭ 613 (48)
13211 L·molϪ1·cmϪ1. Molecular weight determination (THF, 28
°C, c ϭ 0.0069 mol·LϪ1): 727.7 g molϪ1. C24H36O6P2PbS (721.8):
calcd. C 39.9, H 5.0; found C 40.0, H 5.1. MS: m/z (%) ϭ 613 (100)
[M Ϫ SPh], 391 (65) [M Ϫ SPh Ϫ3 OEt Ϫ Et Ϫ tBu], FAB-MS:
m/z (%) ϭ 613 (100) [M Ϫ SPh].
[M Ϫ C(H)(SiMe3)2], 406 (39) [M Ϫ C(H)(SiMe3)2 Ϫ Pb].
[{5-tBu-1,3-[P(O)(OEt)2]2C6H3}4·(Pb2F)] [PF6]3·4THF (6): [4-tert-
Butyl-2,6-bis(diethoxyphosphonyl)phenyl]chloroplumbylene
(2)
(0.107 g, 0.165 mmol) was added portionwise, at Ϫ78 °C, to a solu-
tion of TlPF6 (0.055 g, 0.157 mmol) in THF (20 mL). The reaction
mixture was then stirred at Ϫ78 °C under exclusion of light for
140 min. After storage at Ϫ35 °C for 5 d, the suspension was
characterized by 31P NMR spectroscopy. 31P{1H} NMR
(81.02 MHz, D2O capillary): δ ϭ 18.0 [s, 1-tert-butyl-3,5-bis(di-
ethoxyphosphonyl)benzene, 27%], 54.1 (s, 73%). After the suspen-
sion had been filtered through a diatomaceous earth filter, the solu-
tion was once more characterized by 31P NMR spectroscopy.
31P{1H} NMR (161.98 MHz, D2O capillary): δ ϭ 17.9 [s, 1-tert-
butyl-3,5-bis(diethoxyphosphonyl)benzene, 88%], 54.0 (s, 12%).
Crystallization at Ϫ35 °C afforded 0.13 g (29%) of 6 as colorless
crystals. 1H NMR (400.13 MHz, C6D6): δ ϭ 1.14 (s, 9 H, CH3),
1.17 (t, 12 H, CH3), 1.45 (m, 4 H, THF), 3.61 (m, 4 H, THF),
4.10Ϫ4.26 (complex pattern, 8 H, CH2), 8.20 (d, 2 H, aromatics),
8.81 (t, 1 H, aromatics) ppm. 31P{1H} NMR (161.98 MHz, C6D6):
[4-tert-Butyl-2,6-bis(diethoxyphosphonyl)phenyl](diisopropylamino)-
plumbylene (4). Method A: A solution of iPr2NLi in hexane/diethyl
ether (3:1) (37 mL, 0.75 ) was added, at Ϫ78 °C, to a solution
of
1-tert-butyl-3,5-bis(diethoxyphosphonyl)benzene
(7.5 g,
18.5 mmol) in THF (120 mL) and the reaction mixture was stirred
at this temperature for 5 h. PbCl2 (3.85 g, 13.8 mmol) was added
portionwise and the suspension stirred for 16 h (Ϫ78 to Ϫ30 °C).
After filtration some of the solvent (75 mL) was evaporated. Crys-
tallization at Ϫ6 °C afforded 2·THF [1.98 g (20%)]. The solvent
was then evaporated, and the residue dissolved in hexane (50 mL).
After decantation from insoluble 2 and 1-tert-butyl-3,5-bis(di-
ethoxyphosphonyl)benzene, the solvent was removed in vacuo to
give 4.18 g of a yellow oil containing 4 (yield 45%, purity 83%) and
residues of 2 (δ31P ϭ 52.0 ppm, 5%) and 1-tert-butyl-3,5-bis(di-
ethoxyphosphonyl)benzene (δ31P ϭ 18.4 ppm, 12%). 1H NMR
(400.13 MHz, C6D6): δ ϭ 0.98 (t, 6 H, CH3), 1.13 (s, 9 H, CH3),
1.22 (t, 6 H, CH3), 1.53 [s, 6 H, C(H)(CH3)2], 1.55 [s, 6 H,
C(H)(CH3)2], 3.68Ϫ3.79 (complex pattern, 2 H, CH2), 3.86Ϫ3.97
(complex pattern, 2 H, CH2), 4.17Ϫ4.34 (complex pattern, 4 H,
CH2), 5.12Ϫ5.28 (sept, 2 H, CH), 8.20 (complex pattern, 2 H, aro-
matics) ppm. 13C{1H} NMR (100.61 MHz, C6D6): δ ϭ 16.4 (com-
δ
ϭ 18.8 [s, 1-tert-butyl-3,5-bis(diethoxyphosphonyl)benzene],
Ϫ142.3 (PF6Ϫ) ppm. IR (KBr, inert): ν˜(PϭO) ϭ 1197 cmϪ1, ν˜(OH)
not observed. ESMS: m/z ϭ 1039 [Pb ϩ F ϩ 2 1-tert-butyl-3,5-
bis(diethoxyphosphonyl)benzene]ϩ; 713 [Pb ϩ 3 1-tert-butyl-3,5-
bis(diethoxyphosphonyl)benzene]2ϩ; 510 [2 Pb ϩ 4 1-tert-butyl-3,5-
bis(diethoxyphosphonyl)benzene]4ϩ
; 407 [1-tert-butyl-3,5-bis(di-
ethoxyphosphonyl)benzene ϩ H]ϩ. Elemental analysis and the
melting point of 6 were obtained after THF had been removed
under reduced pressure (11 Torr). C72H128F19O24P11Pb2 (2493.9):
calcd. C 34.6, H 5.2; found C 34.2, H 5.0.
3
plex pattern, JC,P ϭ 7 Hz, 4 C, CH3), 30.1 [s, 3 C, C(CH3)3], 31.0
[s, 4 C, C(H)(CH3)2], 34.7 (s, 1 C, C), 53.7 (s, 2 C, CH), 62.1 (d, 2
C, 2JC,P ϭ 5 Hz, CH2), 62.3 (d, 2 C, 2JC,P ϭ 6 Hz, CH2), 134.8 (dd,
4
1
2JC,P ϭ 17, JC,P ϭ 4 Hz, 2 C, C-3,5), 136.1 (dd, JC,P ϭ 197,
The 1H, 13C, and 31P NMR spectra of compound 4 and the 1H,
13C, 31P, and 207Pb NMR spectra of compound 5 are available.[2]
3JC,P ϭ 26 Hz, 2 C, C-2,6), 148.9 (t, 3JC,P ϭ 13 Hz, 1 C, C-4), 236.8
(t, JC,P ϭ 38 Hz, 1 C, C-1) ppm. 31P{1H} NMR (161.98 MHz,
2
X-ray Crystallographic Study: Intensity data for the colorless crys-
C6D6): δ ϭ 41.7 (s, JP,Pb ϭ 116 Hz) ppm. IR (KBr): ν˜(PϭO) ϭ
1203 cmϪ1. Method B: A solution of LDA in hexane/diethyl ether
(3:1) (0.4 mL, 0.75 ) was added, at Ϫ78 °C, to a suspension of [4-
tert-butyl-2,6-bis(diethoxyphosphonyl)phenyl]chloroplumbylene
(2) (0.187 g, 0.289 mmol) in THF (15 mL). After the reaction mix-
ture had been stirred for 4 h at this temperature, it was charac-
terized by 31P NMR spectroscopy. 31P{1H} NMR (81.02 MHz,
D2O capillary): δ ϭ 18.4 [s, 1-tert-butyl-3,5-bis(diethoxyphosphon-
yl)benzene, 5%], 41.7 (s, JP,Pb ϭ 122 Hz, 4, 83%), 52.0 (s, 2, 12%).
tals were collected with a Nonius KappaCCD diffractometer with
˚
graphite-monochromated Mo-Kα (0.71073 A) radiation at 173(1)
K. The data collection covered almost the whole sphere of the re-
ciprocal space with 3 collections at different k angles with 244 (2),
305 (3), and 260 (6) frames via w rotation (∆/ω ϭ 1°) at two times
15 s (2), 20 s (3), and 30 s (6) per frame. The crystal-to-detector
distance was 3.4 cm. Crystal decay was monitored by repeating the
initial frames at the end of the data collection. Analysis of the
duplicate reflections revealed no indication of any decay. The struc-
[4-tert-Butyl-2,6-bis(diethoxyphosphonyl)phenyl]{[bis(trimethyl- ture was solved by direct methods SHELXS-97[63] and successive
silyl)]methyl}plumbylene (5): LiCH(SiMe3)2 (0.181 g, 1.09 mmol)
was added portionwise, at Ϫ78 °C, to a suspension of [4-tert-butyl-
2,6-bis(diethoxyphosphonyl)phenyl]chloroplumbylene (2) (0.679 g,
1.05 mmol) in THF (50 mL). After the reaction mixture had been
stirred for 16 h (Ϫ78 to Ϫ30 °C), it was filtered. Evaporation of
the solvent then afforded 0.20 g (25%) of 5 as a pale yellow oil. 1H
difference Fourier syntheses. Refinement was applied with full-ma-
trix least-squares methods SHELXL-97.[64] H atoms were placed
in geometrically calculated positions using a riding model with Uiso
constrained at 1.2 for non-methyl and at 1.5 for methyl groups
times Ueq of the carrier C atom. In 3 a disordered ethoxy group
was found with occupancies of 0.6 [C(14)] and 0.4 [C(14Ј)]. In 6
Eur. J. Inorg. Chem. 2003, 3563Ϫ3571
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3569