TY - JOUR
T1 - Preparation, crystal structures, and spectroscopic and redox properties of nickel(II) complexes containing phosphane-(amine or quinoline)-type hybrid ligands and a nickel(I) complex bearing 8-(diphenylphosphanyl)quinoliney
AU - Hashimoto, Akira
AU - Yamaguchi, Hiroshi
AU - Suzuki, Takayoshi
AU - Kashiwabara, Kazuo
AU - Kojima, Masaaki
AU - Takagi, Hideo D.
PY - 2010
Y1 - 2010
N2 - Nickel(II) complexes containing P-N-type bidentate hybrid ligands of 2-aminoethylphosphanes (RR'Pea; RR' = Ph2 or MePh) or 8-quinolylphosphanes (RR'Pqn), namely [Ni(P-N)2](BF4) 2 [P-N = Ph2Pea (1), MePhPea (2), Ph2Pqn (3), or MePhPqn (4)] have been prepared, and their structural, spectroscopic, and electrochemical properties determined. The crystal structure analysis indicates that: the 2-amlnoethylphosphane complexes (1 and 2) have a square-planar coordination geometry around the NiII center with a cis(P,P) configuration, whereas the 8-quinolylphosphane complexes (3 and 4) exhibit a severe tetrahedral distortion because of the steric repulsion between the ortho-H atoms in the mutually cis-positioned quinolyl rings, Complexes 1 and 2 maintain their diamagnetic square-planar four-coordinate structure on acetonitrile solution, whereas complexes 3 and 4 show paramagnetic behavior. Spectroscopic and electrochemical measurements suggest that the ligand-field strengths of these four PN-type ligands increase in the order Ph2Pqn (3) < MePhPqn (4) < Ph2Pea (1) < MePhPea (2). The Ph 2Pqn complex 3 is readily reduced by Zn powder to afford the corresponding nickel(I) complex [Ni(Ph2Pqn)2]BF 4 (5), The crystal structure of complex 5 reveals that the Ni I ion adopts a distorted tetrahedral coordination geometry with slightly longer (≈ 0.05 Å) Ni-P and. Ni-N bond lengths than those in the corresponding NiII complex 3.
AB - Nickel(II) complexes containing P-N-type bidentate hybrid ligands of 2-aminoethylphosphanes (RR'Pea; RR' = Ph2 or MePh) or 8-quinolylphosphanes (RR'Pqn), namely [Ni(P-N)2](BF4) 2 [P-N = Ph2Pea (1), MePhPea (2), Ph2Pqn (3), or MePhPqn (4)] have been prepared, and their structural, spectroscopic, and electrochemical properties determined. The crystal structure analysis indicates that: the 2-amlnoethylphosphane complexes (1 and 2) have a square-planar coordination geometry around the NiII center with a cis(P,P) configuration, whereas the 8-quinolylphosphane complexes (3 and 4) exhibit a severe tetrahedral distortion because of the steric repulsion between the ortho-H atoms in the mutually cis-positioned quinolyl rings, Complexes 1 and 2 maintain their diamagnetic square-planar four-coordinate structure on acetonitrile solution, whereas complexes 3 and 4 show paramagnetic behavior. Spectroscopic and electrochemical measurements suggest that the ligand-field strengths of these four PN-type ligands increase in the order Ph2Pqn (3) < MePhPqn (4) < Ph2Pea (1) < MePhPea (2). The Ph 2Pqn complex 3 is readily reduced by Zn powder to afford the corresponding nickel(I) complex [Ni(Ph2Pqn)2]BF 4 (5), The crystal structure of complex 5 reveals that the Ni I ion adopts a distorted tetrahedral coordination geometry with slightly longer (≈ 0.05 Å) Ni-P and. Ni-N bond lengths than those in the corresponding NiII complex 3.
KW - Ligand effects
KW - N,p ligands
KW - Nickel
KW - Phosphane ligands
UR - http://www.scopus.com/inward/record.url?scp=74049137532&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=74049137532&partnerID=8YFLogxK
U2 - 10.1002/ejic.200900767
DO - 10.1002/ejic.200900767
M3 - Article
AN - SCOPUS:74049137532
SP - 39
EP - 47
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
SN - 1434-1948
IS - 1
ER -