Organometallics p. 870 - 875 (1993)
Update date:2022-08-25
Topics:
Hsiao, Yui-May
Chojnacki, Stephen S.
Hinton, Pamela
Reibenspies, Joseph H.
Darensbourg, Marcetta Y.
The X-ray crystal structures and electrochemical properties as well as chemical reactivity of the thioether complexes [Ni(Ph2PCH2CH2SEt)2][BF 4]2 (5) and [Ni(Ph2PCH2CH2SCH2CH 2CH2SCH2CH2PPh2)][BF 4]2 (6), [Ni(PSSP)]2+, are compared with the thiolate Ni(Ph2PCH2CH2S)2 (4). Complex 4 crystallized in the orthorhombic space group Pbca (No. 61) with a = 9.204(2) ?, b = 15.766(3) ?, c = 17.177(3) ?, V = 2492.6(8) ?3, Z = 4, and final R = 0.050 (Rw = 0.050) for 2212 unique reflections. Complex 5 crystallized in the monoclinic space group P21/c, with a = 10.267(2) ?, b = 13.102(2) ?, c = 13.263(2) ?, β = 93.750(10)°, V = 1780.3(5) ?3, Z = 2, and final R = 0.076 (Rw = 0.072) for 1777 unique reflections. The square-planar structures of 4 and 5 have sulfur donors in a trans arrangement and show a 0.04-? lengthening of both the Ni-S and Ni-P bonds on going from the thiolate to the thioether complex. Within the CH3CN solvent window, the cyclic voltammograms of 5 and 6 show two reversible redox events assigned to NiII/I and NiI/0, whereas the thiolate 4 shows only a sulfur-based irreversible oxidation and no reduction. Complexes 5 and 6 can be chemically reduced to Ni0 species, 5R and 6R, with Na/Hg amalgam. The 1H NMR spectra of the reduced complexes indicate loss of one thioether donor for 5R and both for 6R. Protonation of the reduced species produced a Ni-H and reaction with both CH3I or CH3C(=O)Cl gave rise to Ni-CH3 and NiC(O)CH3 functionalities, respectively. The tetradentate derivatives [HNi(PSSP)]+ and [CH3Ni(PSSP)]+ are more stable than their bidentate analogues and show loss of reversible redox activity; i.e., the cyclic voltammograms find no evidence for stable NiI-H or NiI-CH3, or for NiIII-H or NiIII-CH3 species. The NiC(O)CH3 compounds rapidly and reversibly decarbonylate in solution (at temperatures >-30°C). A contrast of the abilities of structurally analogous P-SR vs N-SR ligands to stabilize subvalent nickel and organonickel functionalities is made.
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