RESOLUTION OF A PLANAR-CHIRAL PLATINUM(II) COMPLEX - CRYSTAL AND MOLECULAR-STRUCTURE OF ]-(-[PTCL(ACHIRAPHOS)(R-PMENPH(2))]PF6[ACHIRAPHOS= ERISK,S-ASTERISK)-2,3-BIS(DIPHENYLPHOSPHINO)BUTANE 2-BETA,5-ALPHA)]-DIPHENYLMENTHYLPHOSPHINE]()(589))
P. Gugger et al., RESOLUTION OF A PLANAR-CHIRAL PLATINUM(II) COMPLEX - CRYSTAL AND MOLECULAR-STRUCTURE OF ]-(-[PTCL(ACHIRAPHOS)(R-PMENPH(2))]PF6[ACHIRAPHOS= ERISK,S-ASTERISK)-2,3-BIS(DIPHENYLPHOSPHINO)BUTANE 2-BETA,5-ALPHA)]-DIPHENYLMENTHYLPHOSPHINE]()(589)), Inorganic chemistry, 32(25), 1993, pp. 5692-5696
The new meso ligand (R,S*)-2,3-bis(diphenylphosphino)butane (achiraph
os) has been synthesized and used to prepare the prochiral square-plan
ar meso complex [PtCl2(achiraphos)]. Displacement of one or the other
of the enantiotopic chlorine atoms in the complex with [1R-(1 alpha,2
beta,5 alpha)]-diphenylmenthylphosphine (R-PMenPh(2)), and subsequent
treatment of the intermediate salts with ammonium hexafluorophosphate,
affords the diastereomeric complexes [SP-4-2-A]- and [SP-4-3-C]-[PtCl
(achiraphos)(R-PMenPh(2))]PF6, which are epimeric at planar-chiral pla
tinum(II). The homochiral SP-4-2-A epimer, C50H57ClF6P4Pt, [alpha](589
)+22.4 degrees (c0.85, acetone), crystallizes in the orthorhombic spac
e group P2(1)2(1)2(1) with a = 9.900(3) Angstrom, b = 15.559(4) Angstr
om, c = 32.789(10) Angstrom, Z = 4, R = 0.036, and R(w) = 0.042 for 38
05 unique data having I> 3 sigma(I). The geometry around the platinum
atom in the complex is square-planar with the R-PMenPh(2) ligand situa
ted trans to the diphenylphosphino group attached to the S carbon of t
he achiraphos. The optically pure complex is configurationally stable
in solution in the absence of chloride.