Heterotopic As,S,P and As,S,As Ligands
1251
Synthesis of 1,3-(AsPh2)22-2-StBu-C6H3 (3)
Acknowledgements
Financial support provided by programs co-financed by the Sectoral Oper-
ational Program Human Resources Development, Contract POSDRU 6/1.5/
S/3, ‘Doctoral Studies: Through Science Towards Society’ (PhD grants for
M.B.S. and I.S.), from the Deutscher Akademischer Austausch Dienst
(DAAD scholarship for I.S., SOE program, Stability Pact for South Eastern
Europe) and the EU-COST Action CM0802 PhoSciNet is gratefully
acknowledged. We thank Chemetall GmbH for kindly providing
n-butyllithium.
Compound 3 was synthesized similarly to compound 2.
n-Butyllithium (2.1M solution in n-hexane, 1.99 mL,
4.18 mmol) was added dropwise to an ice-cold solution of
2-(tert-butylthio)phenyldiphenylarsine (1b) (1.65 g, 4.18 mmol)
in n-hexane (75 mL), and then TMEDA (0.66 g, 5.69 mmol)
was slowly added (over 45 min). The reaction mixture was
stirred for 20 h and allowed to attain room temperature, leading
to the formation of a pale-yellow suspension. The yield of the
metallation step was considered to be 90 %. The reaction vessel
was cooled in an ice bath and a solution of Ph2AsCl (1.00 g,
3.76 mmol) in n-hexane (10 mL) was slowly added (2–3 h) to
the stirred suspension. The solution was stirred for 24 h and
hydrolysed with degassed 5 % aqueous NaOH. The organic
phase was separated and the aqueous phase was extracted with
diethyl ether. The combined organic phases were dried over
MgSO4. After filtration, the solution was concentrated slowly
under vacuum to half its volume to give 3 as a very fine white
precipitate. Crystals of 3 suitable for single-crystal X-ray dif-
fraction analysis were obtained from a two-layer diethyl ether/
n-hexane system at room temperature over 2 days.
References
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Yield 0.63 g (27 %), mp 172–1738C. nmax (KBr)/cmꢀ1
3067 (m), 3051 (m), 2956 (m), 2889 (m), 1950 (w), 1883 (w),
1814 (w), 1580 (m), 1480 (m), 1432 (s), 1363 (m), 1304 (m),
1262 (w), 1159 (m), 1073 (m), 1023 (m), 1000 (m), 913 (w),
848 (w), 785 (s), 734 (s), 696 (s), 527 (m), 480 (m), 471 (m),
418 (w). dH 7.41 (m, 8 H, aryl H), 7.19 (m, 14 H, aryl H), 6.84
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t
(t, JH,H 7.6, 1 H, aryl H), 1.65 (s, 9 H, Bu). dC 152.6, 144.0,
134.9, 134.8, 133.9, 130.1, 128.6 (m), 77.7, 50.7, 32.4. m/z (EI)
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622 ([M]þ, 5 %), 564.9 ([M ꢀ Bu], 20 %), 336.9 ([M ꢀ
t
tBuꢀAsPh2]þ, 63 %), 258.8 ([M ꢀ Buꢀ4Ph]þ, 41 %), 226.9
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Synthesis of 1-AsPh2-2-SH-3-PPh2-C6H3 (4)
A solution of 2 (1.32 g, 2.28 mmol) in THF (20 mL) was added
to a cold (08C) lithium naphthalenide solution, generated from
lithium (39.7 mg, 5.73 mmol) and naphthalene (0.62 g,
4.86 mmol) in THF (30 mL). The reaction mixture was stirred
for 3 h at 08C and then anhydrous HCl (3 mL, 2 M solution in
diethyl ether) was added. The solution was concentrated under
vacuum, and n-pentane (30 mL) was added to the remaining oily
mass. A white precipitate (LiCl) was separated from the pale
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was obtained as a waxy pale-yellow solid and was further
purified by washing with n-pentane. Compound 4 crystallized
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1 week.
Yield 0.79 g (66 %), mp 166–1678C. nmax (KBr)/cmꢀ1 3051
(m), 2964 (w), 2467 (w), 1952 (w), 1882 (w), 1811 (w), 1581
(w), 1479 (m), 1434 (s), 1366 (s), 1305 (w), 1262 (s), 1183 (m),
1095 (s), 1024 (s), 913 (w), 803 (s), 739 (s), 695 (s), 544 (w), 501
(m), 445 (w), 422 (w). dH 7.33 (m, 8 H, aryl H), 7.03 (m, 14 H,
aryl H), 6.68 (t, 3JH,H 7.5, 1 H, aryl H), 4.75 (d, 4JP,H 4.5, 1 H,
SH). dC 143.5 (d, JC,P 28.6), 142.3, 139.0, 138.7 (d, JC,P 9.7),
136.0 (d, JC,P 10.6), 134.4 (d, JC,P 25.9), 134.2, 134.0, 128.8,
128.7 (d, JC,P 7.0), 128.5, 127.7 (m), 126.5. dP ꢀ11.7 (s). m/z
(ESI) 521.0 ([M ꢀ H]þ. Anal. calc. for C30H24AsPS: C 67.98,
H 4.63. Found: C 67.96, H 4.61 %.
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[25] (a) SHELX includes SHELXS-97, SHELXL-97: G. M. Sheldrick, Acta