(Mu-eta2:eta2-disulfido)dinickel(II) complexes supported by 6-methyl-TPA ligands.
A series of (mu-eta(2):eta(2)-disulfido)dinickel(II) complexes 2(n) have been synthesized by the reaction of Na(2)S(2) and nickel(II) complexes 1(n) supported by tris[(pyridin-2-yl)methyl]amine (TPA; 1(0)) [(6-methylpyridin-2-yl)methyl]bis[(pyridin-2-yl)methyl]amine (Me(1)TPA; 1(1)), bis[(6-methylpyridin-2-yl)methyl][(pyridin-2-yl)methyl]amine (Me(2)TPA; 1(2)) and tris[(6-methylpyridin-2-yl)methyl]amine (Me(3)TPA; 1(3)), respectively, and characterised by UV-vis and resonance Raman spectroscopy. X-ray crystallographic analyses on 2(2) and 2(3) supported by Me(2)TPA and Me(3)TPA, respectively, have revealed that the Ni(2)S(2) core is largely bent (approximately 30 degrees) along the S-S axis, being in sharp contrast to the planar Ni(2)S(2) core structure of the (mu-eta(2):eta(2)-disulfido)dinickel(II) complexes reported so far. The UV-vis spectra of 2(0) and 2(1) supported by TPA and Me(1)TPA, respectively, exhibiting an intense absorption band at approximately 360 nm together with a shoulder around 400 nm and a weak and broad absorption band around 450-600 nm, are very close to those of 2(2) and 2(3), suggesting that 2(0) and 2(1) also exhibit a similar distorted Ni(2)S(2) core structure. Resonance Raman spectra of 2(n) showed a characteristic S-S stretching vibration mode at approximately 450 cm(-1) with an isotope shift Delta nu((32)S-(34)S) = 10-15 cm(-1). The reaction of 2(n) with (p-Me-C(6)H(4))(3)P gave (p-Me-C(6)H(4))(3)P=S quantitatively based on 2(n). Hammett analysis on the sulfur atom transfer process from 2(n) to the phosphine derivatives [(p-X-C(6)H(4))P; X = OMe, Me, H and Cl] has indicated that the reaction involves an electrophilic ionic mechanism. Moreover, the order of reactivity of 2(n) toward PPh(3) has been found as 2(0) > 2(3) > 2(1) > 2(2). On the basis of these results, the ligand effects of Me(n)TPA on the structure and reactivity of the nickel(II) complexes have been discussed.
Department of Chemistry, Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka, 558-8585, Japan.
Masayuki
M
Inosako
Atsushi
A
Kunishita
Minoru
M
Kubo
Takashi
T
Ogura
Hideki
H
Sugimoto
Shinobu
S
Itoh
D018360:Crystallography, X-Ray; D007700:Kinetics; D008024:Ligands; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*; D013057:Spectrum Analysis; D013440:Sulfides / Q000737:chemistry
D008024:Ligands; D009942:Organometallic Compounds; D011725:Pyridines; D013440:Sulfides; C431843:tris(2-pyridylmethyl)amine; D009532:Nickel; C033479:sodium sulfide