154560-49-3Relevant academic research and scientific papers
Nickel Thioether Chemistry: Synthesis, Structures and Electrochemistry of Five-co-ordinate Nickel(II) Complexes of aneS3. Crystal Structures of aneS3)(dppm)>2, aneS3)(dcpe)>2*1.25MeCN and aneS3)(tdpme)>2 aneS3 = 1,4,7-Trithiacyclononane ...>
Blake, Alexander J.,Gould, Robert O.,Halcrow, Malcolm A.,Scroeder, Martin
, p. 2909 - 2920 (1993)
Reaction of >L-L = Ph2PCH2PPh2 (dppm), R2PCH2CH2PR2 , cis-Ph2PCH=CHPPh2 (dppv), Ph2PCH2CH2CH2PPh2 (dppp) or MeC(CH2PPh2)3 (tdpme)> with 1 molar equivalent of 1,4,7-trithiacyclononane(aneS3) afforded the complex cations aneS3)(L-L)>(2+).The crystal structures of aneS3)(dppm)>2, aneS3)(dcpe)>2*1.25MeCN and aneS3)(tdpme)>2 showed five-co-ordinate complexes with distorted square-pyramidal geometries about the nickel(II) centres with S-donors of aneS3 occupying two basal and the apical position, Ni-Sapical 2.40-2.65 Angstroem, Ni-Sbasal 2.22-2.27 Angstroem, Ni-Pbasal 2.17-2.22 Angstroem.The complex aneS3)(dppm)>2 crystallises in triclinic space group P, a = 10.9748(25), b = 13.9702(20), c = 15.7688(24) Angstroem, α = 80.071(7), β = 70.817(8), γ = 76.441(8) deg, Dc = 1.374 g cm-3, Z = 2; aneS3)(dcpe)>2*1.25MeCN crystallises in triclinic space group P, a = 12.432(8), b = 13.382(4), c = 15.070(6) Angstroem, α = 86.83(2), β = 70.47(2), γ = 77.28(2) deg, Dc = 1.445 g cm-3, Z = 2; aneS3)(tdpme)>2 crystallises in monoclinic space group Cc, a = 10.7597(16), b = 37.399(5), c = 13.104(3) Angstroem, β = 103.746(11) deg, Dc = 1.491 g cm-3, Z = 4.Cyclic voltammetry of the complexes aneS3)(L-L)>2 in MeCN (0.1 mol dm-3 NBu4PF6) at 293 K at platinum electrodes showed one chemically reversible and one quasi-reversible one-electron reduction at 1E1/2 = -0.77 to -1.16 V, ΔEp = 61-92 mV, 2E1/2 = -1.31 to -1.93 V vs. ferrocene-ferrocenium.On the basis of ESR and electronic spectroscopy, these reduction products are asiigned as pyramidal d9 nickel(I) aneS3)(L-L)>(1+) with binding of both P-donors retained, and tetrahedral 210 nickel(0) aneS3)(L-L)>(0) species respectively.The reaction of aneS3)(L-L)(1+) with CO in MeCN is discussed.
