Unprecedented Metal-Free C(sp³)−C(sp³) Bond Cleavage: Switching fromN-Alkyl- toN-Methyl-1,3,5-triaza-7-phosphaadamantane

Abstract

N-Alkyl-1,3,5-triaza-7-phosphadamantane halides [PTA-R]X (X ) I -, Br -) with more than two carbon atoms in the alkyl chain are shown to easily convert, under mild conditions in aqueous medium, into the corresponding N-methyl derivatives, thus representing a novel type of metal-free C(sp 3 )-C(sp 3 ) bond cleavage that affects inert, unstrained, and unbranched aliphatic groups. This unusual transformation is promoted by Cu ions and is proposed to occur via a postulated ammonium ylide. In the presence of Cu ions, this C-C bond dissociation is also a key point for the formation of a unique 2D Cu(I) coordination polymer with a rare P,N-coordination mode of the PTA cage.

Two in one: Charged tertiary phosphines held together by ionic or covalent interactions as bidentate phosphorus ligands for synthesis of half-sandwich Ru(II)-complexes

“…Already at the time of the first synthesis of pta it was established that it can be methylated on one of the N-atoms by MeI [18]. In addition, several cationic pta-R derivatives were obtained by longer chain alkyl iodides (EtI [19], nPrI [20], nBuI [21] [27].…”

Synthesis, Structural, and Cytotoxic Properties of New Water-Soluble Copper(II) Complexes Based on 2,9-Dimethyl-1,10-Phenanthroline and Their One Derivative Containing 1,3,5-Triaza-7-Phosphaadamantane-7-Oxide

“…A series of Cu(I)-dmphen complexes stabilized by tertiary phosphines and other Cu(II)-dmphen coordination compounds have been also reported, but their poor solubility in polar solvents eventually prevented the application of these compounds as bioactive materials [38,39]. In particular, some of us have reported a number of water-soluble copper(I/II)-PTA-cage coordination networks [10,[40][41][42][43][44] as well as a discrete complexes [32,[40][41][42][43][45][46][47][48], which were evaluated successfully for their magnetic [10,43,45], catalytic [10,44], and luminescent properties [40,42,44,48].…”

Copper(II) and Sodium(I) Complexes based on 3,7‐Diacetyl‐1,3,7‐triaza‐5‐phosphabicyclo[3.3.1]nonane‐5‐oxide: Synthesis, Characterization, and Catalytic Activity

“…[5,6] The reported examples of Cu complexes based on PTA-type ligands are mainly Cu I complexes,e ven if Cu II salts were used as the startingm aterials as ar esult of the tendency of PTAl igands to stabilizet he lower oxidation state of the metal. [7][8][9][10] Among the large family of open-cage PTAd erivatives, [2,11] 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) is ar elevant one (Figure 1), [11a, 12] and its binding capacity has been intensively studied for the Cu, Ru, Rh, Pd, Pt, and Au transition metals to produce complexes that are used mainly for biological applications [13][14][15][16] and, to al esser extent, for catalysis. [17][18][19][20] The DAPTAl igand usually exhibits the P-coordination modet ot he metal center, [12][13][14][15][20][21][22][23] and recently,t he N-coordination mode wasa lso reported.…”

“…Thereafter, coordination polymers based on PTA with mixed‐valence Cu I /Cu II were published . The reported examples of Cu complexes based on PTA‐type ligands are mainly Cu I complexes, even if Cu II salts were used as the starting materials as a result of the tendency of PTA ligands to stabilize the lower oxidation state of the metal …”