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Octa( μ 3 ‐selenido)hexarhenium( III ) Complexes Containing Axial Monodentate Diphosphine or Diphosphine–Monoxide Ligands
Author(s) -
Chen ZhongNing,
Yoshimura Takashi,
Abe Masaaki,
Tsuge Kiyoshi,
Sasaki Yoichi,
Ishizaka Shoji,
Kim HaengBoo,
Kitamura Noboru
Publication year - 2001
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20011015)7:20<4447::aid-chem4447>3.0.co;2-o
Subject(s) - chemistry , phosphine , denticity , ligand (biochemistry) , octahedron , crystallography , luminescence , steric effects , stereochemistry , iodide , carbon monoxide , crystal structure , inorganic chemistry , catalysis , materials science , organic chemistry , biochemistry , receptor , optoelectronics
A series of the octahedral hexarhenium( III ) complexes containing a variable number of diphosphine (diphos) or diphosphine–monoxide (diphosO) ligands have been prepared by the substitution of the diphosphine Ph 2 P(CH 2 ) n PPh 2 ( n =1 to 5) for the iodide ions in the parent octahedral hexarhenium cluster compound [Re 6 Se 8 I 6 ] 3− . The diphosphine Ph 2 P(CH 2 ) n PPh 2 ligands adopt an η 1 ‐bonding mode with the Re 6 ( μ 3 ‐Se) 8 core, and the P donor atom in the pendant arm is noncoordinated and oxygenated in most cases. The series of new hexarhenium( III ) complexes have been well‐defined by 1 H, 13 C, and 31 P NMR spectroscopic and FAB‐MS data. Four compounds among the series were characterized by X‐ray structural determination. Geometrical isomers were identified by NMR spectroscopy as well as by the structural determinations. The apical ligand substitution induces significant change in the redox potentials and the photophysical properties of the Re 6 ( μ 3 ‐Se) 8 core. The E 1/2 value of the reversible process Re III 6 /Re III 5 Re IV becomes more positive with the increasing number of the coordinated P donors. The phosphine‐substituted hexarhenium( III ) derivatives are highly luminescent, with microsecond scale emissive lifetime at ambient temperature, and the fully substituted derivatives with the formula [Re 6 Se 8 ( η 1 ‐diphosO) 6 ] 2+ display the strongest luminescence with the longest emission lifetimes.