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Synthesis, Chemistry, and Catalytic Activity of Ruthenium Diaminodiphosphane Complexes − Crystal Structures of trans ‐[RuCl 2 { κ 3 ‐Ph 2 PC 6 H 4 CH=NC 6 H 10 N(H)CH 2 C 6 H 4 PPh 2 }(PPh 3 )] and cis ‐[RuCl 2 { κ 4 ‐Ph 2 PC 6 H 4 CH=NC 6 H 10 N(H)CH 2 C 6 H 4 PPh 2 }]
Author(s) -
Wong WaiKwok,
Chen XiaoPing,
Pan WeiXiong,
Guo JianPing,
Wong WaiYeung
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(20021)2002:1<231::aid-ejic231>3.0.co;2-w
Subject(s) - chemistry , toluene , catalysis , acetone , nitrogen , medicinal chemistry , ruthenium , dichloromethane , mesitylene , atmosphere (unit) , crystal structure , inorganic chemistry , organic chemistry , physics , solvent , thermodynamics
The interaction of [RuCl 2 (PPh 3 ) 3 ] with one equivalent of N , N ′‐bis[2‐(diphenylphosphanyl)benzyl]‐1 R ,2 R ‐cyclohexanediamine [1 R ,2 R ‐P(NH)(NH)P] in dichloromethane at room temperature gave trans ‐[RuCl 2 { κ 3 ‐1 R ,2 R ‐P(NH)(NH)P}(PPh 3 )] ( 1 ). When heated under reflux in toluene under a nitrogen atmosphere, 1 was converted into trans ‐[RuCl 2 { κ 4 ‐1 R ,2 R ‐P(NH)(NH)P}] ( 2 ). However, when 1 was stirred at room temperature in air, it was oxidized to trans ‐[RuCl 2 { κ 3 ‐1 R ,2 R ‐PN(NH)P}(PPh 3 )] ( 3 ). Depending on the reaction conditions, 3 was converted into trans ‐[RuCl 2 { κ 3 ‐1 R ,2 R ‐P(NH)(NH)P=O}(PPh 3 )] ( 4 ) when heated to 80 °C in toluene in air, to cis ‐[RuCl 2 { κ 4 ‐1 R ,2 R ‐PN(NH)P}] ( 5 ) when stirred at room temperature in acetone in air, or to trans ‐[RuCl 2 { κ 4 ‐1 R ,2 R ‐PN(NH)P}] ( 6 ) when heated under reflux in acetone under a nitrogen atmosphere. When heated under reflux in toluene under a nitrogen atmosphere, 5 isomerized to 6 quantitatively. When heated under reflux in mesitylene under a nitrogen atmosphere, 6 was slowly reduced to 2 . The solid state structures of 3 and 5 were ascertained by X‐ray crystallography. Catalytic studies showed that 1 could catalyze the oxidation of alkanes and alkenes with molecular oxygen.