Synthesis, Chemistry, and Catalytic Activity of Ruthenium Diaminodiphosphane Complexes − Crystal Structures oftrans-[RuCl2{κ3-Ph2PC6H4CH=NC6H10N(H)CH2C6H4PPh2}(PPh3)] andcis-[RuCl2{κ4-Ph2PC6H4CH=NC6H10N(H)CH2C6H4PPh2}]

Abstract

The interaction of [RuCl2(PPh3)3] with one equivalent of N,N′‐bis[2‐(diphenylphosphanyl)benzyl]‐1R,2R‐cyclohexanediamine [1R,2R‐P(NH)(NH)P] in dichloromethane at room temperature gave trans‐[RuCl2{κ3‐1R,2R‐P(NH)(NH)P}(PPh3)] (1). When heated under reflux in toluene under a nitrogen atmosphere, 1 was converted into trans‐[RuCl2{κ4‐1R,2R‐P(NH)(NH)P}] (2). However, when 1 was stirred at room temperature in air, it was oxidized to trans‐[RuCl2{κ3‐1R,2R‐PN(NH)P}(PPh3)] (3). Depending on the reaction conditions, 3 was converted into trans‐[RuCl2{κ3‐1R,2R‐P(NH)(NH)P=O}(PPh3)] (4) when heated to 80 °C in toluene in air, to cis‐[RuCl2{κ4‐1R,2R‐PN(NH)P}] (5) when stirred at room temperature in acetone in air, or to trans‐[RuCl2{κ4‐1R,2R‐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.

Aerobic Cleavage of Alkenes and Alkynes into Carbonyl and Carboxyl Compounds

“…A good conversion to benzoic acid from styrene was described by Wong et al using very low amounts of a ruthenium­(II) diaminodiphosphane complex (Scheme ). Nevertheless, pressures of O 2 higher than 3 MPa were required, and the other alkene assayed, 1-hexene, afforded 1,2-hexanediol as the main product . In contrast, 1 atm of O 2 was enough to cleave selectively an extensive range of mono-, 1,1-di-, and 1,2-disubstituted styrene derivatives to the corresponding carbonyls by means of a Fe­(III) species bearing a pyridine bisimidazoline ligand (Scheme ).…”

Aerobic Cleavage of Alkenes and Alkynes into Carbonyl and Carboxyl Compounds

“…A good conversion to benzoic acid from styrene was described by Wong et al using very low amounts of a ruthenium­(II) diaminodiphosphane complex (Scheme ). Nevertheless, pressures of O 2 higher than 3 MPa were required, and the other alkene assayed, 1-hexene, afforded 1,2-hexanediol as the main product . In contrast, 1 atm of O 2 was enough to cleave selectively an extensive range of mono-, 1,1-di-, and 1,2-disubstituted styrene derivatives to the corresponding carbonyls by means of a Fe­(III) species bearing a pyridine bisimidazoline ligand (Scheme ).…”

Synthesis and characterization of silver(I) complexes [AgL]2[BF4]2 and [Ag(OAc)L]∞ [L=(CH2NHCOC2H4PPh2)2]

“…Thus, during the catalytic processes, the intermediate complexes can be stabilized by both the phosphorus and nitrogen donor groups, and when required, can liberate the labile nitrogen donor groups, thus providing vacant sites for substrate coordination. We are interested in the chemistry of diimino-, diamino-and diamidodiphosphine ligands and have shown that these ligands exhibit a very rich coordination chemistry and can behave as bridging, bi-, tri-, and tetra-dentate ligands, depending on the reaction conditions [7][8][9][10]. We have also reported the coordination behavior of diimino-and diamino-diphosphine ligands toward silver(I) salts [11,12].…”

Aerobic Cleavage of Alkenes and Alkynes into Carbonyl and Carboxyl Compounds

“…A good conversion to benzoic acid from styrene was described by Wong et al using very low amounts of a ruthenium­(II) diaminodiphosphane complex (Scheme ). Nevertheless, pressures of O 2 higher than 3 MPa were required, and the other alkene assayed, 1-hexene, afforded 1,2-hexanediol as the main product . In contrast, 1 atm of O 2 was enough to cleave selectively an extensive range of mono-, 1,1-di-, and 1,2-disubstituted styrene derivatives to the corresponding carbonyls by means of a Fe­(III) species bearing a pyridine bisimidazoline ligand (Scheme ).…”

Synthesis and characterization of silver(I) complexes [AgL]2[BF4]2 and [Ag(OAc)L]∞ [L=(CH2NHCOC2H4PPh2)2]

“…Thus, during the catalytic processes, the intermediate complexes can be stabilized by both the phosphorus and nitrogen donor groups, and when required, can liberate the labile nitrogen donor groups, thus providing vacant sites for substrate coordination. We are interested in the chemistry of diimino-, diamino-and diamidodiphosphine ligands and have shown that these ligands exhibit a very rich coordination chemistry and can behave as bridging, bi-, tri-, and tetra-dentate ligands, depending on the reaction conditions [7][8][9][10]. We have also reported the coordination behavior of diimino-and diamino-diphosphine ligands toward silver(I) salts [11,12].…”

Aerobic Cleavage of Alkenes and Alkynes into Carbonyl and Carboxyl Compounds

“…A good conversion to benzoic acid from styrene was described by Wong et al using very low amounts of a ruthenium­(II) diaminodiphosphane complex (Scheme ). Nevertheless, pressures of O 2 higher than 3 MPa were required, and the other alkene assayed, 1-hexene, afforded 1,2-hexanediol as the main product . In contrast, 1 atm of O 2 was enough to cleave selectively an extensive range of mono-, 1,1-di-, and 1,2-disubstituted styrene derivatives to the corresponding carbonyls by means of a Fe­(III) species bearing a pyridine bisimidazoline ligand (Scheme ).…”

Synthesis and characterization of silver(I) complexes [AgL]2[BF4]2 and [Ag(OAc)L]∞ [L=(CH2NHCOC2H4PPh2)2]

“…Thus, during the catalytic processes, the intermediate complexes can be stabilized by both the phosphorus and nitrogen donor groups, and when required, can liberate the labile nitrogen donor groups, thus providing vacant sites for substrate coordination. We are interested in the chemistry of diimino-, diamino-and diamidodiphosphine ligands and have shown that these ligands exhibit a very rich coordination chemistry and can behave as bridging, bi-, tri-, and tetra-dentate ligands, depending on the reaction conditions [7][8][9][10]. We have also reported the coordination behavior of diimino-and diamino-diphosphine ligands toward silver(I) salts [11,12].…”