Synthesis and structures of new sexadentate complexes produced by electrophilic reactions of macrocyclic ligands in their transition metal complexes

Bowman, Kristin; Riley, Dennis P.; Busch, Daryle H.; Corfield, P. W. R.

doi:10.1021/ja00850a060

Cited by 20 publications

(13 citation statements)

References 2 publications

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“…Reduction of the imino group in 4 and 12 with PtO,/H, gives 5 and 13, respectively. In the case of the dimethylamino derivative 5 a mixture of at least four isomers was obtained.…”

Section: Discussionmentioning

confidence: 99%

“…After drying them over P205 in HV. 11.8 g (36 4.75 g (20 mmol) NiC12 6 H20, 3.26 g (20 mmol) 2,6-diacetylpyridine and 4.05 g (20 mmol) 2 were dissolved in 100 ml EtOH/water 1:l. After addition of 1.5 ml acetic acid the solution was heated to about 80" for 36 h whereby the colour changed from red to violet, The solutiofi was concentrated to about 40 ml and 10 ml saturated NaC104-solution and active charcoal were added. After heating to 80" for 10 min the mixture was filtered through Celite.…”

Section: Experimental Partmentioning

confidence: 99%

“…11-heptudecu-1 (I 7), 13,15-trienenickeI(Zl)] diperchforute (13). 4.01 g (7.15 mmol) 12 were dissolved in 200 ml water and hydrogenated with 40 mg PtO2 at 110 atm H2 during 48 h. After filtering off the catalyst 5 ml saturated NaC104-solution were added and the mixture concentrated until the first crystals formed. After cooling these were collected and recrystallized from acetone/ether whereby 2.36 g (58.5%) 13 Measurements.…”

Section: C17h28c12n4ni010mentioning

confidence: 99%

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Metal Complexes with Macrocyclic Ligands. IX. Synthesis and properties of a new class of branched N₄‐macrocycles with an additional ligating group in the side chain

Lotz¹,

Kaden²

1978

Helvetica Chimica Acta

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SummaryIn the presence of Ni2+ the template reaction between 2,6-diacetylpyridine and 4-(2-dimethylaminoethy1)-or 4-(2-hydroxyethyl)-117-diamino-4-azaheptane yields the complexes of either the open-chain ligand (3 and 11) or of the macrocycle (4 and 12). Reduction of the imino group in 4 and 12 with PtO,/H, gives 5 and 13, respectively. In the case of the dimethylamino derivative 5 a mixture of at least four isomers was obtained. These were partially separated by chromatography on Sephadex SP-25 cation exchanger. Through demetalation of the Ni2+ complexes by cyanide the new macrocycles 7 and 14 were isolated, from which the corresponding Zn2+ and Cu2+ complexes were prepared.The macrocyclic Ni2+-complexes 4, 12, 5 and 13 can exist in two forms depending on the pH of the solution. At low pH protonation of the dimethylamino or hydroxy group in the side chain occurs. The metal ion is then bound to the four nitrogen atoms of the macrocycle in a square planar ligand field. At higher pH, however, the dimethylamino or hydroxy group (the last one also in its deprotonated form) can coordinate to one of the axial positions, whereby pseudooctahedral coordination geometry is induced. This reaction can be quantitatively described by a reversible acid-base equilibrium, the pK, of which greatly depends on the nature of the functional group, the degree of unsaturation of the macrocycle and the metal ion.The acid-base reaction and the concomitant structural change are a direct consequence of the unique combination of the rigid and kinetically stable structure of the macrocycle and of the flexible and kinetically labile functional group of the side chain.In most mono-or bicyclic ligands described in the literature the coordinating atoms are an integral part of the ring [2]. Thus rigid structures result which often account for the specific complexation of these ligands with metal ions. In contrast, I ) 2,

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“…Reduction of the imino group in 4 and 12 with PtO,/H, gives 5 and 13, respectively. In the case of the dimethylamino derivative 5 a mixture of at least four isomers was obtained.…”

Section: Discussionmentioning

confidence: 99%

Section: Experimental Partmentioning

confidence: 99%

Section: C17h28c12n4ni010mentioning

confidence: 99%

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Metal Complexes with Macrocyclic Ligands. IX. Synthesis and properties of a new class of branched N₄‐macrocycles with an additional ligating group in the side chain

Lotz¹,

Kaden²

1978

Helvetica Chimica Acta

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“…[Co|6,13-(OH)2-2,3,9,10-Me4 [14]l,3,8,10-tetraeneN4|Br2]Br ([Co(TIM-6,13-(OH)2)Br2]Br). The diamine (4.5 g, 50 mmol) was added to methanol (150 mL), followed by an equimolar amount of HBr (8.15 g of 48% of aqueous HBr).…”

Section: Methodsmentioning

confidence: 99%

“…Caled for CoC14H24N402Br3: C, 29.04; , 4.18; N, 9.68. Found: C, 28.94; H, 4.29; N, 9.79. [Co|6,13-(OH)2-2,3,9,10-Me4 [14]l,3,8,10-tetraeneN4|Br2]BF4…”

Section: Methodsmentioning

confidence: 99%

Synthesis of hydroxy-substituted macrocyclic ligand complexes of cobalt and isolation of a macrocycle precursor

Welsh¹,

Reynolds²,

Henry³

1977

Inorg. Chem.

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A series of macrocyclic ligand complexes of cobalt(II) having bromides in the axial position and containing one or two hydroxyl groups have been synthesized from either biacetyl or benzil and 1,3-propanediamine and l,3-diamino-2-hydroxypropane. By adding one diamine and the diketone followed by Co(II) and the second diamine yields of the unsymmetrical macrocyclic ligands containing one hydroxyl were obtained rather than a statistical distribution of ligands containing the two diamines. A macrocycle precursor from condensation of two benzils with one 1,3-propanediamine was prepared and isolated. This precursor would only react further with a second diamine if Co(II) is present, demonstrating the template nature of the reaction.

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Large Ring Heterocycles: Template Synthesis and Structure

Shanzer

1983

Bulletin des Soc Chimique

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Synthesis and structures of new sexadentate complexes produced by electrophilic reactions of macrocyclic ligands in their transition metal complexes

Cited by 20 publications

References 2 publications

Metal Complexes with Macrocyclic Ligands. IX. Synthesis and properties of a new class of branched N₄‐macrocycles with an additional ligating group in the side chain

Metal Complexes with Macrocyclic Ligands. IX. Synthesis and properties of a new class of branched N₄‐macrocycles with an additional ligating group in the side chain

Synthesis of hydroxy-substituted macrocyclic ligand complexes of cobalt and isolation of a macrocycle precursor

Large Ring Heterocycles: Template Synthesis and Structure

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Synthesis and structures of new sexadentate complexes produced by electrophilic reactions of macrocyclic ligands in their transition metal complexes

Cited by 20 publications

References 2 publications

Metal Complexes with Macrocyclic Ligands. IX. Synthesis and properties of a new class of branched N4‐macrocycles with an additional ligating group in the side chain

Metal Complexes with Macrocyclic Ligands. IX. Synthesis and properties of a new class of branched N4‐macrocycles with an additional ligating group in the side chain

Synthesis of hydroxy-substituted macrocyclic ligand complexes of cobalt and isolation of a macrocycle precursor

Large Ring Heterocycles: Template Synthesis and Structure

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Product

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Metal Complexes with Macrocyclic Ligands. IX. Synthesis and properties of a new class of branched N₄‐macrocycles with an additional ligating group in the side chain

Metal Complexes with Macrocyclic Ligands. IX. Synthesis and properties of a new class of branched N₄‐macrocycles with an additional ligating group in the side chain