210689-50-2

Upstream product

• 603-35-0 triphenylphosphine 
• 174865-79-3 [Pd(μ-Cl)(3-(CHO)C6H3CH=NCy)]2 
• 174865-79-3 ((C₆H₁₁NCHC₆H₃(CHO))PdCl)2 
• 210689-38-6 PdCl(CHOC₆H₃CHNC₆H₁₁)(P(C₆H₅)3) 

Downstream Products

• 210689-65-9 PdCl(C₆H₁₁NCHC₆H₃CHNC₆H₁₁)(P(C₆H₅)3)2 
• 500101-18-8 (C₆H₃(CHO)2)PdCl(P(C₆H₅)3)2 

Relevant academic research and scientific papers

Cyclometallated compounds of Pd(II): C=N to C=O conversion through acid hydrolysis. Crystal and molecular structures of [Pd{2,4-(CHO)2C6H3} (Cl)(PPh3)2] and [Pd[2,4-(CHO)2C6H3}(Cl) (PPh3)2]

Treatment of the chloro-bridged complex [Pd{4-(CHO)C6H3C(H)=NCy}(Cl)]2 (1) with tertiary monophosphines in a 1:4 molar ratio gave the non-cyclometallated monomer complexes [Pd{4-(CHO)C6H3C(H)=NCy}(Cl)(PR3)2] (PR3: (2) PPh3, (3) PEtPh2, (4) PEt2Ph, (5) PMePh2). The crystal structure of 2 is described. Reaction of complexes 2-5 with a mixture of glacial acetic acid-water gave the monomeric complexes [Pd[2,4-(CHO)2C6H3}(Cl)(PR3)2] (PR3 (6), PPh3 (7), PEtPh2 (8), PEt2Ph (9), PMePh2) after cleavage of the C=N group. Complex 6 was characterized crystallographically. Treatment of 1 with the triphosphine bis(2-diphenylphosphinoethyl) phenylphosphine in 1:2 molar ratio gave the mononuclear complex [Pd{4-(CHO)C6H3C(H)=NCy} {Ph2P(CH2)2PPh(CH2)2PPh2-P,P,P}][Cl] (10) in which the phosphine is coordinated through the three phosphorus atoms. Treatment of 10 with a mixture of acetic acid-water also caused cleavage of the C=N bond giving the complex [Pd{2,4-(CHO)2 C6H3}{Ph2P(CH2)2PPh(CH2)2PPh2-P,P,P}][Cl] (11).

Reactivity of functionalised cyclometallated complexes of palladium(II). Crystal and molecular structure of [Pd{3-(CHO)C6H3C(H)=NCy}(Br)(PEtPh2)]

Treatment of the cyclometallated complexes [{Pd[3-(CHO)C6H3C(H)=NCy}(X)}2] [X=Cl (1), Br (2), I (3)] with tertiary monophosphines in a complex/phosphine 1:2 or 1:4 molar ratio afforded the halide-bridged cleaved [Pd{3-(CHO)C6H3C(H)=NCy}(X)(L)] (6-17) and non-cyclometallated complexes [Pd{3-(CHO)C6H3C(H)=NCy}(X)(L)2] (18-23) (X=Cl, Br or I; L=PPh3, PEtPh2, PEt2Ph or PMePh2), respectively. Reaction of 6-17 with cyclohexylamine in a complex/amine 1:1 or 1:2 molar ratio gave [Pd{3-(CyC(H)=N)C6H3C(H)=NCy}(X)(L)] (24-28) and the non-cyclometallated [Pd{3-(CyC(H)=N)C6H3C(H)=NCy}(X)(L)(NH2Cy)] (29-32) complexes, respectively. Compounds 18, 19 and 22 gave [Pd{3-(CyC(H)=N)C6H3C(H)=NCy}(X)(PR3) 2] (33-35) with two uncoordinated C=N groups, when treated with cyclohexylamine. Other reaction routes are also discussed. The complexes were characterised by their elemental analysis (C, H, N) and by IR and 31P{1H} and 1H-NMR data, and [Pd{3-(CHO)(C6H3C(H)=NCy}(Br)(PEtPh2)] (12) was characterised crystallographically.