Dithiophosphate and Dithiophosphonate Complexes of Pentacoordinate Nickel (II) Containing the Macrocycle 2, 4, 4-Trimethyl-1, 5, 9-Triazacyclododec-1-Ene ([12] … (original) (raw)

Dithiophosphate and dithiophosphonate complexes of pentacoordinate nickel(II) containing the [Ni([12]aneN 3)] 2' fragment ([12]aneN 3 0/2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene ([12]aneN 3-mc1) and its 9-methyl derivative ([12]aneN 3-mc2)) were prepared by using a 'one-pot' synthesis. This consists of the reaction between the corresponding O ,O ?-dialkyldithiophosphoric acid HS(S)P(OR) 2 or (4-methoxyphenyl)-O-alkyldithiophosphonic acid and the hydroxo precursor [Ni([12]aneN 3)(m-OH)] 2 (PF 6) 2 in the appropriate alcohol ROH (R0/Me, Et, i Pr) as solvent to give [Ni([12]aneN 3)(S 2 P(OR) 2 ](PF 6) 2 or [Ni([12]aneN 3){S 2 P(p-CH 3 OPh)(OR)}](PF 6). Among them, [Ni([12]aneN 3-mc1)(S 2 P(OEt) 2 ](PF 6) (2) and [Ni([12]aneN 3-mc1){S 2 P(p-CH 3 O-Ph)(O i Pr)}](PF 6) (9) were characterised by means of X-ray diffraction measurements on a single crystal. These studies show that the dithiophosphate or dithiophosphonate are bonded to the nickel atom as chelating S ,S-ligands and the nickel atoms are in a distorted square pyramidal geometry. Complex 9 is the first structurally characterised example of an O-alkyldithiophosphonate Ni(II) derivative in a distorted square pyramidal geometry. Analytical (C, H, N, S), spectroscopic (IR, UV Á/Vis and 1 H NMR) and mass spectrometry (FAB) data have been used for structural assignments.