Square planar Cu(<scp>i</scp>) stabilized by a pyridinediimine ligand

Cheung, Pui Man; Berger, Robert; Zakharov, Lev N.; Gilbertson, John D.

doi:10.1039/c6cc00271d

Cited by 25 publications

(20 citation statements)

References 37 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…All liquid reactants were dried with molecular sieves (4 Å), degassed and stored in glovebox. Ligands i PR IP , Me DAB , i Pr DAB , Me PDI 30 and i Pr PDI were prepared according to literature procedures. All reactions were conducted in oven‐dried sealed glass bombs under an atmosphere of argon unless otherwise specified.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Isobenzofuranones by Cobalt Catalyzed [2+2+2] Cycloaddition

et al. 2020

View full text Add to dashboard Cite

show abstract

Section: Methodsmentioning

confidence: 99%

Synthesis of Isobenzofuranones by Cobalt Catalyzed [2+2+2] Cycloaddition

et al. 2020

View full text Add to dashboard Cite

show abstract

“…The ligand derives much of its popularity from the formation of active polymerization catalysts in combination with Fe and Co, as originally reported by Brookhart and Gibson . Since then, combinations with virtually all redox-active first-row transition metals have been studied extensively: for just a few references see V, , Cr, , Mn, − Fe, − Co, ,− Ni, − and Cu. − Many of these studies have focused on ligand-centered redox activity and/or olefin polymerization (the latter reported not only for Fe and Co but also for Cr and V , complexes). Surprisingly, only a single paper mentions the combination of DIP with titanium.…”

Section: Introductionmentioning

confidence: 99%

Balance between Metal and Ligand Reduction in Diiminepyridine Complexes of Ti

2017

View full text Add to dashboard Cite

Reaction of the diiminepyridine ligand Et DIP (2,6-Et 2 -C 6 H 3 NCMe) 2 C 5 H 3 N) with TiCl 3 (THF) 3 gave the corresponding Ti(III) complex ( Et DIP)TiCl 3 (1). Reduction of 1 with 1 equiv of KC 8 produced the formally Ti(II) complex ( Et DIP)TiCl 2 (2). From this, ( Et DIP)TiClR complexes (R = Me (3a), Me 3 SiCH 2 (3b), Ph (3c)) were obtained by addition of 1 equiv of RLi. Similarly, dialkyl complexes ( Et DIP)TiR 2 (R = Me (4a), Me 3 SiCH 2 (4b)) were obtained with 2 equiv of RLi. All new complexes except 3b were characterized by single-crystal X-ray diffraction. EPR studies indicate that complex 1 is best regarded as a true Ti(III) complex with an "innocent" DIP ligand. Complexes 2−4 are all diamagnetic. In contrast to DIP complexes of the late transition metals Fe and Co, the new complexes 2−4 show strong upfield 1 H NMR shifts for the pyridine β and γ protons caused by transfer of negative charge to the DIP ligand. On the basis of this and the CN and C imine −C Py bond lengths, a description involving Ti(IV) and a dianionic ligand seems most appropriate, and DFT calculations support this interpretation. This means that reduction of Ti(III) complex 1 results in oxidation of the metal center to Ti(IV). VT-NMR studies of 4a suggest a small and temperature-dependent thermal population of a triplet state, and indeed calculations indicate that 4a has the lowest singlet− triplet energy difference of the systems studied.

show abstract

“…Both of them are much longer than those of any other Cu-N bonds in 3, and close to the Cu-N van der Waals radii limit (2.95Å). 17 In contrast to nearly planar congurations of sphz 6À in 1, two acylhydrazine wings of each sphz 6À in 3 twists with each other. Two such "V" shaped sphz 6À ligands thus cross together with their notches face to face, and use their donors in notches to chelate two Cu 2+ ions (Cu2 and Cu5) synergistically.…”

Section: Resultsmentioning

confidence: 98%

“…Both of them are much longer than those of any other Cu–N bonds in 3, and close to the Cu–N van der Waals radii limit (2.95 Å). 17 …”

Section: Resultsmentioning

confidence: 99%

A family of 3d metal clusters based on N–N single bonds bridged quasi-linear trinuclear cores: the Mn analogue displaying single-molecule magnet behavior

Wang

Tang

et al. 2018

RSC Adv.

View full text Add to dashboard Cite

The reactions of the diacylhydrazine ligands N,N 0 -bisalicyl-2,6-pyridine dicarbohydrazide (H 6 sphz) and6-pyridine dicarbohydrazide (H 6 msphz) with various 3d metal salts, afforded a series of coordination clusters, namely, [Mn III 2 Mn II (sphz)(acac) 2 (CH 3 OH) 4 ] (1, acac À ¼ acetylacetone anions), [Ni II 3 (msphz)(Py) 4 ] (2, Py ¼ pyridine), [Cu II 6 (sphz) 2 (Py) 4 ] (3) and [Cu II 6 (msphz) 2 (Py) 4 ]$2DMF$2H 2 O (4). Cluster1 and 2 are single ligand assembled quasi-linear trinuclear structures. Both 3 and 4 consist a pair of quasi-linear {Cu 3 } cores, which are linked together by two crossed ligands. The adjacent 3d metal ions in all trinuclear cores of 1-4 are bridged by N-N single bonds of ligands, which convey ferromagnetic (FM) interactions between 3d metal centers of 1, and antiferromagnetic (AFM) interactions between those of 2-4. In particular, the FM interactions and linear arrangement of mixed-valence Mn centers in 1 result in a large spin ground states value (S T ) of 13/2, as well as single-molecule magnet (SMM) behavior of slow relaxation and hysteresis of magnetization.

show abstract

Square planar Cu(i) stabilized by a pyridinediimine ligand

Cited by 25 publications

References 37 publications

Synthesis of Isobenzofuranones by Cobalt Catalyzed [2+2+2] Cycloaddition

Synthesis of Isobenzofuranones by Cobalt Catalyzed [2+2+2] Cycloaddition

Balance between Metal and Ligand Reduction in Diiminepyridine Complexes of Ti

A family of 3d metal clusters based on N–N single bonds bridged quasi-linear trinuclear cores: the Mn analogue displaying single-molecule magnet behavior

Contact Info

Product

Resources

About