Pd complexes of (RR)- and (SS)-1,5-methylbenzyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane as catalysts in alternating cooligomerization of CO with dienes

Abstract

Alternating copolymerization of CO with norbornadiene and ethylidenenorbornene is studied in the presence of Pd complex with ( SS )-1,5-methylbenzyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane ligand. The structure of cooligomers formed and cooligomerization rate are shown to depend on the catalytic system composition and comonomer structure. The obtained cooligomers are characterized by structural methods.

Hydrogen Oxidation and Production Using Nickel-Based Molecular Catalysts with Positioned Proton Relays

“…Reaction of 5a with [Ni(CH 3 CN) 6 ](BF 4 ) 2 in acetonitrile results in a 90% yield of the red complex [Ni(P Ph 2 N Ph 2 ) 2 (CH 3 CN)](BF 4 ) 2 , 6a , step 2 of reaction 1. The nitrate salt has been reported previously 31b. The reaction of formaldehyde, cyclohexylphosphine, and benzylamine produced a mixture of the desired cyclic ligand P Cy 2 N Bz 2 , 5b , and polymeric material, and further reaction of this mixture with [Ni(CH 3 CN) 6 ](BF 4 ) 2 yielded the purple complex [Ni(P Cy 2 N Bz 2 ) 2 ](BF 4 ) 2 , 6b in 34% yield.…”

“…Synthesis and Characterization of Nickel Complexes with Positioned Pendant Bases. The synthesis of the cyclic ligand 5a (P Ph 2 N Ph 2 , 1,3,5,7-tetraphenyl-1,5-diaza-3,7-diphosphacyclooctane) from formaldehyde, phenylphosphine, and aniline, as shown in step 1 of reaction 1, was carried out using literature methods 31a. Reaction of 5a with [Ni(CH 3 CN) 6 ](BF 4 ) 2 in acetonitrile results in a 90% yield of the red complex [Ni(P Ph 2 N Ph 2 ) 2 (CH 3 CN)](BF 4 ) 2 , 6a , step 2 of reaction 1.…”

1,3,6‐Azadiphosphacycloheptanes: A novel type of heterocyclic diphosphines

“…Most of these compounds include only one phosphorus center [16][17][18], but the condensation of hydroxymethyl derivatives of 1,2-diphosphinoethane and 1,2-diphosphinobenzene with amino acids led to the bicyclic diphosphines, where bridgehead phosphorus atoms are included simultaneously into the sevenand eight-membered heterocycles [19]. The complexes of 1,5-diaza-3,7-diphosphacyclooctanes with different transition metals (Cu I [9,20,21], Re I [12], Pt II [9,12,13,22], and Pd II [9,[12][13][14]) were synthesized, and the structure of these complexes in the solid state and dynamic processes in solution as well as catalytic activity in the hydrogenation of alkynes [23], copolymerization of alkenes and carbon monoxide [24] have been studied. Although the chelating type of the coordination was predominant [9,[12][13][14][20][21][22], these diphosphines appeared to be also able to form the binuclear complexes as the bridging ligands in spite of the cis-mutual orientation of the electron lone pairs on the phosphorus atoms [9,22].…”