Synthesis and Properties of Dimetallic Complexes Based on a New Oxalamidine-Derived Ligand System with Pendant Pyridine Functionality

Abstract

Reaction of sterically hindered bis(imidoyl)chlorides of oxalic acid with picolylamine afforded conformationally locked oxalic acid‐derived amidines with pendant pyridine functionalities. Based on this new multivalent ligand system, dimetallic complexes were efficiently prepared.

Synthesis and characterisation of aluminium and magnesium complexes supported by pendant oxalic amidinate ligands

“…No intra-or inter-molecular hydrogen bonds are found in this structure. However complex and broad signals, which are normally observed except in compound with intramolecular hydrogen bonds, 35 were found in the 1 H NMR. In order to study the tautomeric rotation of amidine, variable temperature NMR experiments of an analytically pure sample of compound 1 in toluene-d 8 were investigated.…”

Synthesis and characterisation of aluminium and magnesium complexes supported by pendant oxalic amidinate ligands

“…No intra-or inter-molecular hydrogen bonds are found in this structure. However complex and broad signals, which are normally observed except in compound with intramolecular hydrogen bonds, 35 were found in the 1 H NMR. In order to study the tautomeric rotation of amidine, variable temperature NMR experiments of an analytically pure sample of compound 1 in toluene-d 8 were investigated.…”

Calcium complexes containing oxalamidinate ligands as catalysts for ε-caprolactone polymerization

“…ε-Caprolactone (Acros) was dried over magnesium sulfate and distilled under reduced pressure before use. HCl•H 2 N-(CH 2 ) 2 SMe, 18 [PhNvC{NH(CH 2 ) 2 OMe}-C{NH(CH 2 ) 2 OMe}v NPh] (1), 12e [PhNvC{NH(CH 2 ) 2 NMe 2 }-C{NH(CH 2 ) 2 NMe 2 }v NPh] (2), 12e N 1 ,N 2 -bis(2,4,6-trimethylphenyl) oxaldiimidoyl dichloride, 14 [Ph TriMe NvC{NHCH 2 Py}-C{NHCH 2 Py}v NPh TriMe ] (5) 14 and Ca{N(SiMe 3 ) 2 } 2 (THF) 2 6f were prepared by literature methods.…”

“…Due to the ease of preparation and better controlled character, complex 8 was introduced to examine the living and immortal characters under optimized conditions. Experimental results exhibited that complex 8 can work as a catalyst to initiate high monomer-toinitiator ratios in the presence of benzyl alcohol accompanied by increasing temperature and volume, with high conversions of CL even up to [CL] 0 /[Ca] 0 ratios of 1000, yielding PCLs with a molecular weight as large as 114 000 in 240 min (entries [14][15][16][17][18]. The linear relationship between the number-average molecular weight (M n ) and the monomer-to-initiator ratio ([M] 0 /[I] 0 ) demonstrated in Fig.…”

“…The degree of polymerization indicated by this spectrum (n = 16, M n (ms) = 1958 g mol −1 ) is in good agreement with the experimental value and the mass spectrum shows a cluster of homologous peaks separated by a molecular mass of ∼114 Da corresponding to one ε-caprolactone repeating unit. No evidence for cyclic 1) 2.3620( 16), Ca-N(2) 2.3736( 16), Ca-N(3) 2.5565( 17), Ca-O 2.4348( 14), Ca-N(4) 2.3358( 16), C(7)-C(7A) 1.540 (14), N( 1…”

Simultaneous Cation/Anion Coordination by Bifunctional 1,2-Diimine/1,2-Diamine Type Ligands: Synthesis, Structures, and Properties of Tight Ion Pair Complexes of Ruthenium and Iron

“…General: p-Tolyl oxalic amidine ligand (oxam1); [30] the ligand N,NЈ-bis(2-pyridylmethyl)-1,2-bis(2,4,6-trimethylphenylimino)ethane-1,2-diamine (oxam2), [20,31] and [(tbbpy) 2 Ru]Cl 2 and [(tbbpy) 2 Ru-(bbimH 2 )](X) 2 (X ϭ Cl, PF 6 ) [3,29] were prepared according to described methods. The complexes (η 6 -p-cymene)RuCl 2 , PdCl 2 (CH 3 CN) 2 , and trifluoroacetic acid (Aldrich) and perfluorooctylcarboxylic acid (ABCR) were used without additional purification.…”

Synthesis and characterisation of aluminium and magnesium complexes supported by pendant oxalic amidinate ligands

“…No intra-or inter-molecular hydrogen bonds are found in this structure. However complex and broad signals, which are normally observed except in compound with intramolecular hydrogen bonds, 35 were found in the 1 H NMR. In order to study the tautomeric rotation of amidine, variable temperature NMR experiments of an analytically pure sample of compound 1 in toluene-d 8 were investigated.…”

Calcium complexes containing oxalamidinate ligands as catalysts for ε-caprolactone polymerization

“…ε-Caprolactone (Acros) was dried over magnesium sulfate and distilled under reduced pressure before use. HCl•H 2 N-(CH 2 ) 2 SMe, 18 [PhNvC{NH(CH 2 ) 2 OMe}-C{NH(CH 2 ) 2 OMe}v NPh] (1), 12e [PhNvC{NH(CH 2 ) 2 NMe 2 }-C{NH(CH 2 ) 2 NMe 2 }v NPh] (2), 12e N 1 ,N 2 -bis(2,4,6-trimethylphenyl) oxaldiimidoyl dichloride, 14 [Ph TriMe NvC{NHCH 2 Py}-C{NHCH 2 Py}v NPh TriMe ] (5) 14 and Ca{N(SiMe 3 ) 2 } 2 (THF) 2 6f were prepared by literature methods.…”

“…Due to the ease of preparation and better controlled character, complex 8 was introduced to examine the living and immortal characters under optimized conditions. Experimental results exhibited that complex 8 can work as a catalyst to initiate high monomer-toinitiator ratios in the presence of benzyl alcohol accompanied by increasing temperature and volume, with high conversions of CL even up to [CL] 0 /[Ca] 0 ratios of 1000, yielding PCLs with a molecular weight as large as 114 000 in 240 min (entries [14][15][16][17][18]. The linear relationship between the number-average molecular weight (M n ) and the monomer-to-initiator ratio ([M] 0 /[I] 0 ) demonstrated in Fig.…”

“…The degree of polymerization indicated by this spectrum (n = 16, M n (ms) = 1958 g mol −1 ) is in good agreement with the experimental value and the mass spectrum shows a cluster of homologous peaks separated by a molecular mass of ∼114 Da corresponding to one ε-caprolactone repeating unit. No evidence for cyclic 1) 2.3620( 16), Ca-N(2) 2.3736( 16), Ca-N(3) 2.5565( 17), Ca-O 2.4348( 14), Ca-N(4) 2.3358( 16), C(7)-C(7A) 1.540 (14), N( 1…”

Simultaneous Cation/Anion Coordination by Bifunctional 1,2-Diimine/1,2-Diamine Type Ligands: Synthesis, Structures, and Properties of Tight Ion Pair Complexes of Ruthenium and Iron

“…General: p-Tolyl oxalic amidine ligand (oxam1); [30] the ligand N,NЈ-bis(2-pyridylmethyl)-1,2-bis(2,4,6-trimethylphenylimino)ethane-1,2-diamine (oxam2), [20,31] and [(tbbpy) 2 Ru]Cl 2 and [(tbbpy) 2 Ru-(bbimH 2 )](X) 2 (X ϭ Cl, PF 6 ) [3,29] were prepared according to described methods. The complexes (η 6 -p-cymene)RuCl 2 , PdCl 2 (CH 3 CN) 2 , and trifluoroacetic acid (Aldrich) and perfluorooctylcarboxylic acid (ABCR) were used without additional purification.…”

Synthesis and characterisation of aluminium and magnesium complexes supported by pendant oxalic amidinate ligands

“…No intra-or inter-molecular hydrogen bonds are found in this structure. However complex and broad signals, which are normally observed except in compound with intramolecular hydrogen bonds, 35 were found in the 1 H NMR. In order to study the tautomeric rotation of amidine, variable temperature NMR experiments of an analytically pure sample of compound 1 in toluene-d 8 were investigated.…”

Calcium complexes containing oxalamidinate ligands as catalysts for ε-caprolactone polymerization

“…ε-Caprolactone (Acros) was dried over magnesium sulfate and distilled under reduced pressure before use. HCl•H 2 N-(CH 2 ) 2 SMe, 18 [PhNvC{NH(CH 2 ) 2 OMe}-C{NH(CH 2 ) 2 OMe}v NPh] (1), 12e [PhNvC{NH(CH 2 ) 2 NMe 2 }-C{NH(CH 2 ) 2 NMe 2 }v NPh] (2), 12e N 1 ,N 2 -bis(2,4,6-trimethylphenyl) oxaldiimidoyl dichloride, 14 [Ph TriMe NvC{NHCH 2 Py}-C{NHCH 2 Py}v NPh TriMe ] (5) 14 and Ca{N(SiMe 3 ) 2 } 2 (THF) 2 6f were prepared by literature methods.…”

“…Due to the ease of preparation and better controlled character, complex 8 was introduced to examine the living and immortal characters under optimized conditions. Experimental results exhibited that complex 8 can work as a catalyst to initiate high monomer-toinitiator ratios in the presence of benzyl alcohol accompanied by increasing temperature and volume, with high conversions of CL even up to [CL] 0 /[Ca] 0 ratios of 1000, yielding PCLs with a molecular weight as large as 114 000 in 240 min (entries [14][15][16][17][18]. The linear relationship between the number-average molecular weight (M n ) and the monomer-to-initiator ratio ([M] 0 /[I] 0 ) demonstrated in Fig.…”

“…The degree of polymerization indicated by this spectrum (n = 16, M n (ms) = 1958 g mol −1 ) is in good agreement with the experimental value and the mass spectrum shows a cluster of homologous peaks separated by a molecular mass of ∼114 Da corresponding to one ε-caprolactone repeating unit. No evidence for cyclic 1) 2.3620( 16), Ca-N(2) 2.3736( 16), Ca-N(3) 2.5565( 17), Ca-O 2.4348( 14), Ca-N(4) 2.3358( 16), C(7)-C(7A) 1.540 (14), N( 1…”

Simultaneous Cation/Anion Coordination by Bifunctional 1,2-Diimine/1,2-Diamine Type Ligands: Synthesis, Structures, and Properties of Tight Ion Pair Complexes of Ruthenium and Iron

“…General: p-Tolyl oxalic amidine ligand (oxam1); [30] the ligand N,NЈ-bis(2-pyridylmethyl)-1,2-bis(2,4,6-trimethylphenylimino)ethane-1,2-diamine (oxam2), [20,31] and [(tbbpy) 2 Ru]Cl 2 and [(tbbpy) 2 Ru-(bbimH 2 )](X) 2 (X ϭ Cl, PF 6 ) [3,29] were prepared according to described methods. The complexes (η 6 -p-cymene)RuCl 2 , PdCl 2 (CH 3 CN) 2 , and trifluoroacetic acid (Aldrich) and perfluorooctylcarboxylic acid (ABCR) were used without additional purification.…”