Alkylamine complexes

The affinity of platinum(II) for N-donor ligands is well established. There are numerous examples in the literature of mono-, di-, and trinuclear platinum(II)-ammine and alkylamine complexes, most of which are structural analogues of the anticancer agent, mplatin (cis- PtCl2(NH3)2]), and the corresponding trans isomer. Selected novel complexes and synthetic methods are presented below. 

In a series of Cr -alkylamine complexes with CrN skeletons, a correlation has been shown to exist between the radiationless transition rate and the number of active hydrogens attached to the donor atoms.The authors also report an expression that predicts the dependence of the non-radiative rates from the vibrational degeneracy and the displacement of the maximum frequency modes. 

Figure 2. Interlayer spacing of the dichalcogenides-n-alkylamines complexes, O observed, and A calculated according to different orientations of the alkyl chain in respect to the slabs (after...

Kiihn, K., Wasgestian, F., and Kupka, H. (1981) The role of hydrogen vibrations in the radiationless deactivation of chromium (Ill)-alkylamine, complexes in their doublet state. J. Phys. Chem.,... 

Dietze, A. and Wasgestian, F. (1986) Deuterium isotope effect in the photophysic of chromium (III) alkylamine complexes. Ber. Bunsenges. Phys. Chem., 90, 111. 

Alkylamines react with leucoquinizarin in a stepwise manner to give l-alh anaino-4-hydroxyanthraquinone, and 1,4-diaLkylamino derivatives after air oxidation. Aromatic amines react similarly in the presence of boric acid as a catalyst. The complex formed (129) causes the less nucleophilic aromatic amines to attack at the 1-, and 4-positions. 

Complex nitrogen compounds are formed from the reaction of aLkylamines with ethylene oxide (61). Thus diethylamine and ethylene oxide react to yield diethylaminoethanol. The diaLkylarninoethanols can react with ethylene oxide to give amino poly(ethylene glycols) ... 

In contrast to pyridine-hydrogen fluoride, which is acidic and acts as a protonating agent, in alkylamine-hydrogen fluoride complexes, fluorine is a nucleophile. The difference of the nature of these two types of reagents has been... 

Poly[bis(amino)phosphazenes] XVI and a series of polyphosphazenes bearing Methoxy-ethoxyethoxy and alkylamine side groups XVII have been synthesized and complexed with LiCl04 by Chen-Yang [623,624]. 

Alkylamination of naphthazarin copper complex (37)22 gives predominantly a mixture of 2(or 3),5-bis(alkylamino)-8-hydroxy-l,4-naphthoquinone (38) and 2,6-bis(alkylamino)-4,8-dihydroxy-l, 5-naphthoquinone... 

In an analogous reaction, urea substrates having alkyl substituents at only one of the N atoms undergo alkylamine elimination to form a dinickel cyanate complex.2081 In contrast, no reaction was observed for A ,A7-dialkylated substrates. 

Platinuni(II) Complexes with Nitrogen-donor Ligands 6.5.4.2.1 Ammine and alkylamine ligands... 

Alkylnickel amido complexes ligated by bipyridine have been prepared that undergo reductive elimination of V-alkyl amines (Equation (54)).207,208 Unlike the phosphine-ligated palladium arylamides, these complexes underwent reductive elimination only after oxidation to nickel(III). Thermally induced reductive elimination of alkylamines from phosphine-ligated nickel complexes appears to occur after consumption of phosphine by arylazides 209... 

More recently, reductive elimination of aryl ethers has been reported from complexes that lack the activating substituent on the palladium-bound aryl group (Equation (55)). These complexes contain sterically hindered phosphine ligands, and these results demonstrate how steric effects of the dative ligand can overcome the electronic constraints of the reaction.112,113 Reductive elimination of oxygen heterocycles upon oxidation of nickel oxametallacycles has also been reported, but yields of the organic product were lower than they were for oxidatively induced reductive eliminations of alkylamines from nickel(II) mentioned above 215-217... 

Another situation is observed when salts or transition metal complexes are added to an alcohol (primary or secondary) or alkylamine subjected to oxidation in this case, a prolonged retardation of the initiated oxidation occurs, owing to repeated chain termination. This was discovered for the first time in the study of cyclohexanol oxidation in the presence of copper salt [49]. Copper and manganese ions also exert an inhibiting effect on the initiated oxidation of 1,2-cyclohexadiene [12], aliphatic amines [19], and 1,2-disubstituted ethenes [13]. This is accounted for, first, by the dual redox nature of the peroxyl radicals H02, >C(0H)02 and >C(NHR)02 , and, second, for the ability of ions and complexes of transition metals to accept and release an electron when they are in an higher- and lower-valence state. 

Symmetrical premetallised 1 2 metal-dye complexes of unsulphonated monoazo structures with aluminium (5.57) or trivalent iron (5.58) have been patented recently for use as solvent dyes [36]. They contain a polar methoxypropylaminosulphone grouping in each diazo component and are marketed as alkylamine salts. It remains to be seen, however, whether a full colour gamut of bright aluminium and iron complex dyes can be discovered with light fastness performance equivalent to that of currently available chromium and cobalt complex dyes. 

Leucoquinizarin can be represented by various tautomers such as structures 6.21 and 6.22 however, 1H- and 13C-n.m.r. have shown the dominant species to be the 2,3-dihydro tautomer (6.22) [7]. Alkylamines react with leucoquinizarin in a stepwise manner to give the corresponding 1,4-dialkylamino derivative (6.23) after air oxidation (Scheme 6.9). The less nucleophilic arylamines do not react unless boric acid is present as a catalyst. The complex thus formed (6.24) is more susceptible to nucleophilic attack at the 1- and 4-positions than is leucoquinizarin. Unsymmetrical 1,4 diaminoanthraquinones can be synthesised by using two different amines the corresponding symmetrical dyes are also formed to a certain extent. 

The stepwise oxidation of alkylamine, which leads to N-dealkylation, generates nitrones that form tightly bound complexes with the heme iron [48]. These heme iron complexes give rise to characteristic changes in the UV-Vis spectrum of the CYP. 

Many dmgs such as verapamil, diltiazem, troleandomydn and erythromycin contain alkylamine groups and are able to form tightly bound complexes, in particular with CYP3A4 [49-53],... 

Compounds containing a benzodioxole moiety are oxidized by CYPs to generate a carbene that forms a tightly bound complex with the heme iron, easily measurable by UV-Vis spectroscopy. There are numerous examples in the literature paroxetine, MDP alkylamines, MDP benzothiazines, MDP benzothiazolines and MDP piperazines (see Scheme 11.2) [54—60],... 

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