1.4.8.11- Tetraazacyclotetradecane complexes

Kimura, E., S. Wada, M. Shionoya, and Y. Okazaki (1994). New series of multifunctionalized nickel(II)-cyclam (cyclam = 1,4,8,11 tetraazacyclotetradecane) complexes. Application to the photoreduction of carbon dioxide. Inorg. Chem. 33, 770-778. 

The characterization, redox properties, and pulse radiolysis study of manganese(III) complexes of type [MnLCy (where L = cyclam, meso-, and rac-5,7,7,12,14,14-hexamethylcyclam (tet a and tet b, respectively)) have been reported." An X-ray crystal structure of the meso-5,l,l, 2, A, A-hexamethyl-l,4,8,ll-tetraazacyclotetradecane complex shows that the coordination geometry of the tet a complex is close to octahedral with the macrocycle coordinated equatorially and the chlorides occupying irons axial sites. 

The monovalent Co chemistry of amines is sparse. No structurally characterized example of low-valent Co complexed exclusively to amines is known. At low potentials and in non-aqueous solutions, Co1 amines have been identified electrochemically, but usually in the presence of co-ligands that stabilize the reduced complex. At low potential, the putative monovalent [Co(cyclam)]+ (cyclam = 1,4,8,11-tetraazacyclotetradecane) in NaOH solution catalyzes the reduction of both nitrate and nitrite to give mixtures of hydroxylamine and ammonia.100 Mixed N-donor systems bearing 7r-acceptor imine ligands in addition to amines are well known, but these examples are discussed separately in Section 6.1.2.1.3. 

The 14-membered macrocycle 1,4,8,11-tetraazacyclotetradecane (cyclam or [14]aneN4), unlike cyclen, is capable of encircling most transition metal ions and in the case of Co111 the trans configuration is much preferred by comparison with the folded cis isomer. Electrochemical reduction of A,v-[Co(cyclam)(OI I)2]+ in 3M NaOH leads to rapid isomerization to the trans form, and the relative stabilities of the trans and cis isomers of the di- and trivalent complexes were determined from a thermodynamic cycle.702 This preference for trans orientation of the non-macrocyclic donors has enabled the isolation and investigation of many Co complexes without the complications of isomerization. Some novel examples include /r[Pg.61]

The first structurally characterized example of a platinum(II) derivative containing a saturated tetraamine macrocycle, 6,13-dimethyl-l,4,8,ll-tetraazacyclotetradecane-6,13-diamine has been reported (80).251 The species crystallizes as the colorless tetra-cationic complex from dilute HC104 solution by slow evaporation, where the two pendant primary amines are protonated. Other macrocyclic tetraamine complexes including [Pt([14]aneN4)]Cl2 have also been described.252... 

Using 1,4,8,11-tetraazacyclotetradecane, the structure of complex (800) (distorted trigonal planar Cu-Cu 6.739 A) was determined. Reactivity with 02 was investigated to demonstrate the formation of trans-l,2-peroxo species.585 As part of their work with copper(I) complexes with 02, the structure of a dicopper(I) complex ((801) distorted tetrahedral 7.04 A), supported by macrocyclic ligand environment, was reported by Comba and co-workers. Tolman and co-workers structurally characterized a three-coordinate copper(I)-phenoxide complex (802) (planar T-shaped) that models the reduced form of GO.587 The copper(I) analogue [Cu(L)][CF3-SO3]-0.43MeOI I (803) of a copper(II) complex (534) was also reported to demonstrate the role of ligand framework conformability in CV /Cu1 redox potentials.434 Wilson and co-workers... 

Complexation and determination of formation constants has been studied with the tetramethyl-cyclam (l,4,8,ll-tetramethyl-l,4,8,ll-tetraazacyclotetradecane) ligand.686 A series of zinc N4 donor macrocyclic complexes with different ring sizes were synthesized and characterized for comparison with cadmium derivatives.687... 

The ligand 6,13-dimethyl-l,4,8,ll-tetra-azacyclotetradecane-6,13-diamine coordinates as a hexadentate ligand to zinc in neutral aqueous solution. Potentiometric titrations were used to determine the stability constant for formation. The pXa values were determined for five of the six possible protonation steps of the hexamine (2.9, 5.5, 6.3, 9.9 and 11.0).697 Studies of the syn and anti isomers of 6,13-dimethyl-1,4,8, ll-tetraazacyclotetradecane-6,13-diamine reveal that they offer different shapes for metal binding, which is reflected in the stability constants for 1 1 zinc ligand ratio complexes. The selectivity of binding to the zinc ion compared to the cadmium(II) ion by both isomers is significant.698... 

An extremely selective electrocatalyst for C02 reduction to CO in water has recently been found by Beley et a/.135 A rather simple Ni complex of 1,4,8,11-tetraazacyclotetradecane, [Ni(II)-cyclam],... 

It is well-established that electroreduced nickel(I) complexes of cyclam and a variety of substituted cyclams add oxidatively to alkyl halides to give alkylnickel(III) complexes in organic solvents,251,276 the lifetime of the carbon-nickel bond governing the overall behavior of the system. However, it was shown that [Ni (tmc)]+ (one-electron reduced form of complex (17) tmc= 1,4,8,11-teramethyl 1,4,8,11-tetraazacyclotetradecane) reacts with alkyl chlorides in aqueous alkaline solution in a one-electron process.277,278... 

A number of novel dioxo variants of the tetraazamacrocycles have been synthesized and stability constants were measured with Cu2+.114 A few of these were further evaluated as chelating agents with 64Cu.115 Structural differences included ring size (from 12 to 14) and placement of the oxo groups. Of the six variations synthesized, only one, l,4,8,ll-tetraazacyclotetradecane-3-9-dione(14N402-3,9), readily formed a complex (Figure 9). 

In most cases, metal ion coordination by a dendrimer takes place by units that are present along the dendrimer branches (e.g., amine, imine, or amide groups) or appended at the dendrimer periphery (e.g., terpyridine, cathecolamide ligands). When multiple identical coordinating units are present, dendrimers give rise to metal complexes of variable stoichiometry and unknown structures. Luminescent dendrimers with a well defined metal-coordinating site have been reported so far [16, 17], and the most used coordination site is 1,4,8,11-tetraazacyclotetradecane (cyclam). 

The Co(III) complexes with the 1,4,8,11-tetraazacyclotetradecane (cyclam) ligand are found to behave as redox mediators for the indirect electroreduction of meso-1,2-dibromo-l,2-diphenylethane (261) leading to tr ns-stilbene (262) in a DMF-Bu4NCl04-(Pt) system (Scheme 98) [400]. 

This class of compounds, which includes 1,4,8,11-tetraazacyclotetradecane (otherwise known as cyclam), consists of a cyclic macrostructure containing four central nitrogen atoms. These nitrogens form a complex with a transition metal, holding it in the center of a square-planar configuration. Often, the cavity size formed by the macrocycle will stabilize one oxidation state of the transition metal over others due to the size of the metal center... 

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