Inorganic Chemistry p. 519 - 526 (1987)
Update date:2022-07-29
Topics:
Montgomery, Craig D.
Payne, Nicholas C.
Willis, Christopher J.
The synthesis of a number of platinum(II) complexes of the hybrid ligand Ph2PCH2C(CF3)2OH (HL1) is described. The ligand interacts with Pt2+ in two ways: either unidentate and neutral, coordinating through phosphine, or bidentate and uninegative, (L1)-, coordinating through phosphine and alkoxide to form a five-membered chelate ring. Complexes prepared include cis- and trans-[PtCl2(HL1)2], cis- and trans-[PtCl(L1)(HL1)], cis-[Pt(L1)2], cis-[PtCl(L1)(PR3)], trans-[Pt(CH3)(L1)(HL1)], and the platinum(IV) complex [PtCl2(L1)2]. Complete crystal and molecular structural determinations have been made on two complexes. trans-[PtCl2(HL1)2] is monoclinic, space group P21/n, with a = 16.934 (2) A, b = 10.320 (1) A, c = 10.198 (2) A, β = 90.32 (1)°, V = 1782.2 (9) A3, and Z = 2. Least-squares refinement on F of 232 variables using 3234 observations converged at a conventional agreement factor of 0.039. cis-[Pt(L1)2] (CHCl3 solvate) is monoclinic, space group P21/c, with a = 20.036 (3) A, b = 10.133 (1) A, c = 19.517 (3) A, β = 109.69 (1)°, V = 3731 (2) Aβ3, and Z = 4. Least-squares refinement on F of 313 variables using 3030 observations converged at a conventional agreement factor of 0.045. Ligand profiles are calculated from the structural data, and monodentate HL1 is assigned a cone angle of 159°; the -CH2C(CF3)2OH substituent on phosphorus has a bulk comparable to that of tert-butyl or -C6F5. The C-OH bond length in coordinated HL1 is 1.388 (7) A, significantly less than those found in unfluorinated alcohols. It is concluded that the bulk of neutral HL1 stabilizes the trans isomer of [PtCl2(HL1)2], while the effect of antisymbiosis is dominant in determining the geometry of complexes where the ligand is bidentate. Mechanisms for the formation and interconversion of the complexes are suggested.
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