Inorg. Chem. 1993, 32, 4812-4818
4812
Optical Resolutions and Chelating Properties of (f)-[2-(Methylsulfinyl)ethyl]diphenylarsine and Its Phosphorus Analogue Simon Y. M. Chooi, Soh-Yun Siah, Pak-Hmg hung,’ and I 15'. The reflections enantiomer. were obtained by an automated random search routine at room Attempted Resdutioa of (*)-2: Formationand Separationof Intend temperature on a Siemens R3m/V four-circle diffractometer using Diastereomers [SP-4-4-(S),(S))and [SP-dQ(R),(a1-Chloro[l-[l-(di graphite monochromated Mo Ka radiation (A = 0.71073 A). A pale methylPmino)ethyl)-2-naphth.lenyl-C,NJ[[2-(methylsdfinyl)ethylJdiyellow crystal of approximate dimensions 0.15 X 0.20 X 0.40 mm was phenylphosphine-PJpahdim(II). A solution of (S)-&CH2C12(6.9 g) in used. Data were collected for 3.0' I 28 I 50' and index range 0 Ih dichloromethane (200 mL) was treated with a solution of (+)-2 (5.0 g) I 12,O 5 k 5 13, -32 I I5 32 with a variable scan rate of 1.50-15.0O in the same solvent. Removal of solvent after 3 h of stirring yielded a min-I. Table I1 gives a summary of the crystallographicdata. A total mixture of [S-(R*,R*)]-7 and [R-(R*,S*)]-7 as a yellow glass (5.5 g, of 5874 reflections were collected and 5079 observed reflections [F > 99% yield): mp 176-178 'c (dec); [a]D +22S0 ( c 1.0, CH2C12); 'H 3u(F)] were used in the refinement. Intensities of three standard ~ CHMe), 2.04 (d, 3H, )JHH NMR (CDCl3) 6 2.04 (d, 3H, 3 J = ~6.3 Hz, reflections were measured after every 97 reflection data were collected; = 6.3 Hz,CHMe),2.55-2.90(m,4H,ZPCH2),2.58 (s,3H,SMe),2.59 no deteriorationin the intensity was detected. Semiempiricalabsorption (s, 3H,SMe), 2.73 (s,6H,2NMe),2.96 (d, ~ H , ' J P H= 4.3 Hz,NMe), corrections were applied. The structure was solved by direct methods ~ 3.7 Hz, NMe), 3.1 1-3.21 (m, 2H, ZSCHH'), 3.252.97 (d, 3H, 4 J p = 3.33 (m, lH, SCHH'), 3.50-3.57 (m, lH, SCHH'), 4.37 (qn, 2H, 3 J ~ ~and non-hydrogen atoms other than Pd were located from Fourier difference maps. All thenon-hydrogen atoms were refined anisotropically. =4 J p= ~ 6.3 Hz, 2CHMe), 6.62-8.17 (m, 32H, aromatics); ILPNMR Hydrogen atoms were introducedat fixed distance (0.960A) from carbon (CDCl3) 6 34.75 (s), 34.98 (9). Anal. Calcd for C29H33ClNOPPdS C, atoms and were assigned fixed thermal parameters. A total of 703 56.5; H, 5.4; N, 2.3. Found: C, 56.5; H, 5.3; N, 2.3. Reaction of 7 (100 parameters were refined. The function minimized during full-matrix mg) in dichloromethane(15 mL) and AgC104 (33 mg) in acetonitrile ( 5 least-squaresrefinement was ZwlF, - Fc12where wI = u2(F) 0.0006Fz mL) over 1 h produced 6 as a mixture of [S-(R*,R*)]- and [R-(R*,S*)]giving R = 0.030, R, = 0.037, and S = 1.08. All calculations were diastereomers in 87% yield (96 me). performed on a Digital Equipment Corp. MicroVax I1 computer using Dichloro((R)-[2-( m e t h y ~ y l ) e t h y l # l i p ~ n y l P r s ~ A ~ ~ m the Siemens SHELXTL PLUS package. (II).24 A solution of (CHsCN)2PdC12 (80 mg) in acetonitrile (20 mL) (100 mg) in the same solvent (10 mL) at room was treated with (a-1 Acknowledgment. This work was supported by grants from temperature for 2 h. After removal of solvent under reduced pressure, the Shaw Foundation (Singapore) and the National University the dark yellow precipitate was recrystallized from acetonitrile/ether of Singapore. Supplemelltpry MaterialAvailable: For (S8,Sc)-6tables of crystaldata, (24) The apparent inversion of configurationof the sulfoxide that takes place data collection,solution and refinement, final positional parameters, bond when sulfur is coordinated to the metal is consistent with the specification distances and angles, anisotropic thermal parameters of non-hydrogen of Cahn-Ingold-Prelog (CIP) sequence rules.25 atoms, and calculated hydrogen parameters (12 pages). Ordering (25) Cahn, R.S.; Ingold, C. K.;Prelog, V. Angew. Chem., I n t . Ed. Engl. 1966, 5, 385-415. information is given on any current masthead page.
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