The unique β-diketiminate ligand in aluminum(<scp>i</scp>) and gallium(<scp>i</scp>) chemistry

Zhong, Ming; Sinhababu, Soumen; Roesky, Herbert W.

doi:10.1039/c9dt04763h

Cited by 130 publications

(120 citation statements)

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“…[22][23][24][25] This reactivity has been comprehensively documented in several recent review articles. 5,20,[26][27][28] Despite the diverse range of reactivity demonstrated by Al(I), up until recently 1 and 2, and a handful of derivatives thereof, have essentially remained the sole examples of stable sources of this powerful reagent. However, problems with their unreproducible and low yielding syntheses have hampered their use in more scalable synthetic procedures.…”

Section: Introductionmentioning

confidence: 99%

Recent advances in low oxidation state aluminium chemistry

2020

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Section: Introductionmentioning

confidence: 99%

Recent advances in low oxidation state aluminium chemistry

2020

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“…[4] Interestingly,t he oxidative addition reaction is not only restricted to TM complexesb ut can be also mediated by other reactive species such as group 13 and group 14 carbenoids. In this sense, the works by Roesky, [5] Nikonov, [6] Crimmin [7] or more recently,Y amasita [8] and co-workers on the oxidative addition of s-bonds to Al I carbenoids are representative examples which nicely illustrate the current growingi nterest in this area of main group chemistry. [9] Compared to the activation of CÀX( X = halogen, heteroatom, hydrogen) bonds, the CÀCb ond cleavage in unstrained arenes, and particularly in benzene, has been much more underdeveloped.…”

Section: Introductionmentioning

confidence: 93%

Rationalizing the Al^I‐Promoted Oxidative Addition of C−C Versus C−H Bonds in Arenes

Cabrera-Trujillo

Fernández

2020

Chemistry A European J

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The factors controlling the oxidative addition of C−C and C−H bonds in arenes mediated by AlI have been computationally explored by means of Density Functional Theory calculations. To this end, we compared the processes involving benzene, naphthalene and anthracene which are promoted by a recently prepared anionic AlI‐carbenoid. It is found that this species exhibits a strong tendency to oxidatively activate C−H bonds over C−C bonds, with the notable exception of benzene, where the C−C bond activation is feasible but only under kinetic control reaction conditions. State‐of‐the‐art computational methods based on the combination of the Activation Strain Model of reactivity and the Energy Decomposition Analysis have been used to rationalize the competition between both bond activation reactions as well as to quantitatively analyze in detail the ultimate factors controlling these transformations.

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“…This has led to a wide scope of applications ranging from the formation of redox‐active systems, enhanced spectroscopic properties, supporting ligands for metal‐mediated catalysis as well as the activation of small molecules . In this regard, β‐diketiminate ligands have been proven capable of supporting metal ions in a number of oxidation states as well as chemical environments . Especially, the stabilization of sub‐valent and uncommon oxidation states, for example, Fe I , Al I , Ga I , Si II , Ge I , and Mg I species, has been an achievement of supporting β‐diketiminate ligand systems.…”

Section: Introductionmentioning

confidence: 99%

A Phosphine Functionalized β‐Diketimine Ligand for the Synthesis of Manifold Metal Complexes

Zovko

Bestgen

Schoo

et al. 2020

Chemistry A European J

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Ab is(diphenyl)-phosphine functionalized b-diketimine (PNac-H) was synthesizeda saflexible ligand for transition metal complexes.T he newly designed ligand features symmetrically placed phosphine moieties around a b-diketimine unit, forming aP NNP-type pocket. Due to the hard and soft donora toms (N vs. P) the ligand can stabilize various coordination polyhedra.Acomplete series rangingf rom coordination numbers2to 6w as realized. Linear,t rigonal planar,s quare planar,t etrahedral, square pyramidal,a nd octahedral coordination arrangements containing the PNacligand around the metal centerw ere observed by using suitable metal sources. Hereby, PNac-H or its anion PNac À acts as mono-, bi-and tetradendate ligand. Such ab road flexibility is unusualf or ar igid tetradentate system.T he structural motifs were realized by treatment of PNac-H with as eries of late transitionm etal precursors, for example, silver,g old, nickel, copper, platinum, and rhodium. The new complexes have been fully characterizedb ys ingle crystal X-ray diffraction, NMR,I R, UV/Vis spectroscopy,m ass spectrometry as well as elemental analysis. Additionally,s elected complexes were investigated regarding their photophysical properties. Thus,P Nac-H provedt ob ea ni deal ligand platform for the selectivec oordination and stabilization of variousm etal ions in diversepolyhedra and oxidation states. sis [8, 19-23] as well as the activation of small molecules. [13, 24-26] In this regard, b-diketiminate ligandsh ave been proven capable of supporting metal ions in an umber of oxidation states as well as chemical environments. [27] Especially,t he stabilization of sub-valent andu ncommon oxidation states,f or example, Fe I , [26] Al I , [24, 27, 28] Ga I , [27] Si II , [29] Ge I , [30] and Mg I species, [31, 32] has been an achievement of supporting b-diketiminatel igand systems. Hereby,t he scaffold can be easily modified by varying the corresponding N-substituents,w hicha re adjustable regarding their steric demand, electronic properties as well as the introductiono fa dditional functionalities. [15] Thiso ffers ah igh degreeo fc ontrol for task-specific adjustments, for example, the kinetic stabilization of sub-valent and reactive metal species via sterically demanding substituents, [31, 33, 34] or an enhanced reactivity of the resulting metal complexes. [35, 36] In general,ab-diketiminate ligand provides am onoanionic, bidentate support for metal ions, [15] yet the introduction of additional heteroatom donor sites to the b-diketiminate scaffold allowst he extension to more complex coordination motifs,a higherd egree of metal stabilization as wella st he potential formation of heterobimetallicc omplexes.H erein, the design of the ligand plays ac rucial role in promoting or enforcingspecific arrangements. The introduction of additional side groups to a b-diketimines ystemh as already been investigatedapplying O-donora nd S-donorf unctionalities (Figure1), enabling the formation of multidentate ONNO and SNNS pockets, respectively.T hese bifunctionall ...

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The unique β-diketiminate ligand in aluminum(i) and gallium(i) chemistry

Cited by 130 publications

References 103 publications

Recent advances in low oxidation state aluminium chemistry

Recent advances in low oxidation state aluminium chemistry

Rationalizing the Al^I‐Promoted Oxidative Addition of C−C Versus C−H Bonds in Arenes

A Phosphine Functionalized β‐Diketimine Ligand for the Synthesis of Manifold Metal Complexes

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The unique β-diketiminate ligand in aluminum(i) and gallium(i) chemistry

Cited by 130 publications

References 103 publications

Recent advances in low oxidation state aluminium chemistry

Recent advances in low oxidation state aluminium chemistry

Rationalizing the AlI‐Promoted Oxidative Addition of C−C Versus C−H Bonds in Arenes

A Phosphine Functionalized β‐Diketimine Ligand for the Synthesis of Manifold Metal Complexes

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Rationalizing the Al^I‐Promoted Oxidative Addition of C−C Versus C−H Bonds in Arenes