Tris-(2-pyridylmethyl)amine-ligated Cu(ii) 1,3-diketonate complexes: anaerobic retro-Claisen and dehalogenation reactivity of 2-chloro-1,3-diketonate derivatives

Abstract

Six-coordinate Cu(ii) diketonate complexes were isolated and characterized; TPA-ligated Cu(ii) chlorodiketonate derivatives exhibit anaerobic retro-Claisen reactivity.

Light-induced O2-dependent aliphatic carbon–carbon (C–C) bond cleavage in bipyridine-ligated Co(ii) chlorodiketonate complexes

“…Synthetic systems that enable studies of divalent metal-mediated O 2 -dependent aliphatic carbon–carbon bond cleavage within a diketonate ligand remain rare. 5,6,12,13 In this regard, studies of the oxidative cleavage of divalent metal chlorodiketonate complexes as a function of the metal ion are a novel approach toward examining the effect of metal ion on O 2 activation and aliphatic C–C cleavage. 6 As summarized in Scheme 5, at ambient temperature under air, complexes 1 , 5 and 8 are stable with respect to O 2 .…”

“…5,6,12,13 In this regard, studies of the oxidative cleavage of divalent metal chlorodiketonate complexes as a function of the metal ion are a novel approach toward examining the effect of metal ion on O 2 activation and aliphatic C–C cleavage. 6 As summarized in Scheme 5, at ambient temperature under air, complexes 1 , 5 and 8 are stable with respect to O 2 . It should be noted that the Ni( ii ) and Co( ii ) chlorodiketonate complexes 1 and 8 are coordinatively saturated, whereas the Cu( ii ) complex 5 exhibits a five-coordinate metal center in the solid state.…”

“…In fact, there are very few well-characterized first-row metal diketonate complexes that are known to exhibit reactivity with O 2 and undergo aliphatic C–C bond cleavage . 5,6 To date, a Co( ii ) diketonate complex which undergoes O 2 -dependent aliphatic C–C bond cleavage within the diketonate moiety has not been reported.…”

“…As an approach for investigating the O 2 reactivity of metal diketonate complexes, our laboratory has pursued studies of first-row metal divalent metal chlorodiketonate complexes. 6 A mononuclear Ni( ii ) p -methoxy-substituted chlorodiketonate complex ( 1 , Scheme 1(a)) supported by an aryl-appended tris(2-pyridylmethyl)amine ligand is stable with respect to O 2 under ambient conditions. However, oxidative C–C bond cleavage occurs within the diketonate unit upon illumination with UV light (350 nm) under aerobic conditions.…”

Crystal structure of bis(1,8-dibenzoyl-7-methoxynaphthalen-2-yl)terephthalate: Terephthalate phenylene moiety acts as bidentate hydrogen acceptor of bidirectional C-H···π non-classical hydrogen bonds

“…Weak interactions in the solid of organic molecular substances have acquired interests and the revaluation in the scientific area over the last two decades [1][2][3]. Indeed, weak interactions have been established as essential features in influencing the chemical, physical, and biological activity properties of materials [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21], by determining their threedimensional single molecular structure and spatial organization of molecular assembly. A number of papers and reviews have been dedicated to the crystallographic and theoretical study and consequently the analysis of halogen interactions and nonclassical hydrogen bonds such as C-H•••X (X = Polar atom) and C-H•••π hydrogen bonds have drastically increased over recent years, emphasizing the applicability and usefulness of weak interactions to scientific disciplines [22][23][24][25][26][27][28][29][30].…”