TY - JOUR
T1 - Osmium(VI)-Dioxo Complexes Derived from β-Diketone Schiff Bases and Their Reactivity with Arene- and Alkanethiols. Synthesis, Characterization, Structures, and Electrochemical Data
AU - Lynch, W. E.
AU - Lintvedt, R. L.
AU - Shui, X. Q.
PY - 1991/3/1
Y1 - 1991/3/1
N2 - Novel trans-dioxoosmium(VI) complexes derived from dibasic tetradentate Schiff-base ligands obtained from the condensation of β-diketones and ethylenediamine have been synthesized. Reduction of these Os(VI) complexes with thiols yields Os(IV) products with trans thiolate ligands. The synthesis, characterization, and electrochemical properties of the Os(VI) oxo and Os(IV) thiolato complexes are described. Cyclic voltammetry was used to investigate the cathodic reduction and anodic oxidation potentials of the complexes. The substantial effect of the thiolate substituent on the reversible reduction potential (E1/2) of the Os(IV)-Os(III) couple has been investigated. The reduction potential of the couple shifts anodically for more acidic thiols and cathodically for less acidic thiols. The trend in E1/2 is correlated to the delocalization ability of the thiol ligand. A single-crystal X-ray structure determination has been completed for OsVIO2[(BA)2en] (1), recrystallized by slow diffusion from dichloromethane/diethyl ether. Crystal data: P[formula-omitted], a = 10.880 (1) Å,b= 12.634 (2) Å, c = 14.902 (2) Å, a = 78.64 (l)°, β = 81.60 (l)°, γ = 72.559 (9)°, Z = 4, V = 2058.6 (5) Å3, R = 0.0391, Rw = 0.0295. A crystal structure of OsIV(SCH2C6H5)2[(BA)2en] (5) was also completed. Single crystals were obtained from dichoromethane/diethyl ether. Crystal data: P[formula-omitted], a = 10.864 (6) Å, b = 17.903 (3) Å, c = 17.988 (4) Å, a = 89.57 (2)°, β = 77.20 (3)°, γ = 84.67 (3)°, Z = 4, V = 3395 (2) Å3, R = 0.0375, Rw = 0.0255.
AB - Novel trans-dioxoosmium(VI) complexes derived from dibasic tetradentate Schiff-base ligands obtained from the condensation of β-diketones and ethylenediamine have been synthesized. Reduction of these Os(VI) complexes with thiols yields Os(IV) products with trans thiolate ligands. The synthesis, characterization, and electrochemical properties of the Os(VI) oxo and Os(IV) thiolato complexes are described. Cyclic voltammetry was used to investigate the cathodic reduction and anodic oxidation potentials of the complexes. The substantial effect of the thiolate substituent on the reversible reduction potential (E1/2) of the Os(IV)-Os(III) couple has been investigated. The reduction potential of the couple shifts anodically for more acidic thiols and cathodically for less acidic thiols. The trend in E1/2 is correlated to the delocalization ability of the thiol ligand. A single-crystal X-ray structure determination has been completed for OsVIO2[(BA)2en] (1), recrystallized by slow diffusion from dichloromethane/diethyl ether. Crystal data: P[formula-omitted], a = 10.880 (1) Å,b= 12.634 (2) Å, c = 14.902 (2) Å, a = 78.64 (l)°, β = 81.60 (l)°, γ = 72.559 (9)°, Z = 4, V = 2058.6 (5) Å3, R = 0.0391, Rw = 0.0295. A crystal structure of OsIV(SCH2C6H5)2[(BA)2en] (5) was also completed. Single crystals were obtained from dichoromethane/diethyl ether. Crystal data: P[formula-omitted], a = 10.864 (6) Å, b = 17.903 (3) Å, c = 17.988 (4) Å, a = 89.57 (2)°, β = 77.20 (3)°, γ = 84.67 (3)°, Z = 4, V = 3395 (2) Å3, R = 0.0375, Rw = 0.0255.
UR - http://www.scopus.com/inward/record.url?scp=0004276559&partnerID=8YFLogxK
U2 - 10.1021/ic00005a026
DO - 10.1021/ic00005a026
M3 - Article
AN - SCOPUS:0004276559
SN - 0020-1669
VL - 30
SP - 1014
EP - 1019
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 5
ER -