Syntheses and Reactions of the Cis-PtCl2{Ph2P(CH2CH2O)nCH2CH2PPh2-P, P'} (n = 3-5) Metallacrown Ether Complexes. The x-ray Crystal Structures of the n = 4 and 5 Complexes and of [Cis-Pt{Ph2P(CH2CH2O)4CH2CH2PPh2-P, P', O}(H2O)](BF4)2

Academic Article

Abstract

  • Metallacrown ether complexes of the type PtCl (Ph P(CH CH O) CH CH PPh } (n = 3-5) have been prepared and characterized by C and P NMR spectroscopy. A single complex is formed with the n = 3 and 4 ligands, and one major and two minor complexes are formed with the n = 5 ligand. X-ray crystal structures of the n = 4 and major n = 5 complexes have been obtained (n = 4: monoclinic space group P2 /n; a = 12.798 (1), b = 16.4875 (9), c = 16.726 (1) Å β = 104.003 (6)° V = 3424.4 Å ; Z = 4. n = 5: monoclinic space group P2 /c; a = 12.9220 (9), b = 15.5925 (8), c = 18.3271 (5) Å β = 92.540 (5)°, V= 3689.0 Å ; Z = 4). The metallacrown ether rings in both complexes exhibit similar conformations. The cavity in the n = 4 complex appears to be of the appropriate size for binding Li+ and that in the n = 5 complex appears to be of the appropriate size for binding Na+. The complexes do appear to coordinate alkali metal cations, but these reactions are complicated by solubility differences and by loss of the chlorides. The n = 4 complex reacts with AgBF to yield the cationic [Pt(Ph P(CH CH O)4CH CH PPh -P, P', O)(H O)](BF ) complex. The X-ray crystal structure of this complex has been determined (triclinic space group Pi; a = 9.971 (2), b = 10.293 (2), c = 20.212 (5) Å; α = 80.92 (2), β = 84.92 (2), γ = 75.48 (1)° V = 1980.3 Å ; Z = 2). The Ph P(CH CH O) CH CH PPh ligand is coordinated to the platinum through both phosphines and one ether oxygen and is also hydrogen bonded to the platinum-coordinated water through two other ether oxygens. © 1992, American Chemical Society. All rights reserved. 2 2 2 2 n 2 2 2 1 1 4 2 2 2 2 2 2 2 4 2 2 2 2 4 2 2 2 13 31 3 3 3
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    Author List

  • Varshney A; Webster M; Gray G
  • Start Page

  • 2580
  • End Page

  • 2587
  • Volume

  • 31
  • Issue

  • 12