147105-55-3Relevant academic research and scientific papers
Synthesis and coordination chemistry of 1-phenyl-1-phospha-4,7-dithiacyclononane
Blower, Philip J.,Chadwick, Alan V.,Jeffery, John C.,Mullen, Gregory E. D.,Powell, Anne K.,Salek, Spencer N.,Smith, Raymond J.,Went, Michael J.
, p. 170 - 178 (1999)
Reaction of PhP(CH2CH2SH)2 with 1,2-dichloroethane and Cs2CO3 under high dilution conditions affords 1-phenyl-1-phospha4,7-dithiacyclononane (L) as an oil in 52% yield. The geometry of L has been probed by 1H NMR spectroscopy, which indicates an equilibrium mixture containing gauche S-C-C-S and S-C-C-P segments, and molecular mechanics calculations which find a lowest energy endodentate conformation minimum and also energetically accessible exodentate minima. Endo- and exodentate conformations are observed in the crystal structure of [Cu(η1-L)(η3-L)][PF6] (1) formed by the reaction of L with [Cu(NCMe)4][PF6]. Reaction of Hg(ClO4)2 with L affords [HgL2][ClO4]2 (2) whose structure has also been established by X-ray diffraction. The mercury ion is in a very distorted octahedral environment with two short Hg-P bonds (average 2.404 A) and four long Hg-S bonds (average 3.092 A). Reaction of L with AgBF4 or Ni(BF4)2 or CoBr2 or Fe(BF4)2 affords [AgL2][BF4] (3), [NiL2][BF4]2 (4), [CoL2]Br2 (5) and [FeL2][BF4]2 (6), respectively, which were characterised by FAB mass spectroscopy and elemental analysis. Cyclic voltammetry studies were used to compare the redox properties of 4, 5 and 6 with their trithiacy-clononane (9S3) analogues and in compound 4 the ligand L was found to stabilise Ni in the oxidation states 0, I, II and III. UV-Vis spectroscopic measurements show that L is a stronger field ligand than 9S3. EXAFS studies were also performed on 4, 5 and 6, which established that all three complexes are six-coordinate.
