Cationic Indium Alkyl Complexes Incorporating Aminotroponiminate Ligands

Delpech, Fabien; Guzei, Ilia A.; Jordan, Richard F.

doi:10.1021/om010578x

Cited by 43 publications

(29 citation statements)

References 90 publications

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“…[2] Nevertheless, cooperative behavior has been reported for ATI ligands in the coordination sphere of group 13 metals (Scheme 9). [28,76,77] De-aromatization of the C 7 N 2 moiety [78] has also been reported with a proton as the electrophile: stirring H-ATI iPr/iPr with W(CO) 3 (NCMe) 3 in heptane at 65°C gave compound 20 (Scheme 10). [79] This reaction involves migration of a proton from the nitrogen atom to the C3 position of the ATI ligand.…”

Section: Reactions With Electrophilesmentioning

confidence: 99%

“…The reactivity of ATI ligands towards electrophiles or nucleophiles is considered to be lower than that of the related diazadiene ligands, for instance . Nevertheless, cooperative behavior has been reported for ATI ligands in the coordination sphere of group 13 metals (Scheme ) , , . Reaction of compounds [M(ATI i Pr/ i Pr )R 2 ] ( 17‐M ; M = Al–In; R = alkyl) with a tritylium salt did not proceed via initial abstraction of the alkyl group R. An electrophilic attack in the C‐5 position of the ligand was observed instead, resulting in formation of compounds 18‐M , which can be detected spectroscopically at low temperature (–90 to –45 °C) for M = Al or even isolated in the case of M = Ga, In.…”

Section: Ligand Cooperativitymentioning

confidence: 99%

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New Perspectives for Aminotroponiminates: Coordination Chemistry, Redox Behavior, Cooperativity, and Catalysis

Hanft

Lichtenberg

2018

Eur J Inorg Chem

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Aminotroponiminates (ATIs) are monoanionic ligands with an N,N‐binding pocket and a rigid, planar, unsaturated, C7‐ring as a ligand backbone. Recent findings show that this ligand backbone can play an active role in coordination chemistry, redox reactions, and ligand‐centered reactivity of ATI complexes. Based on these results, ATIs have been recognized as redox‐active and cooperative ligands, which has implications for existing and potential future applications of ATI compounds in synthesis, catalysis, and materials science. The catalytic applications of ATI complexes are summarized in this Microreview, including results from the fields of hydroamination, epoxidation, cyanosilylation, ε‐caprolactone‐, olefin‐, epoxide‐, and epoxide/CO2 (co‐)polymerization as well as electron transfer catalysis. Furthermore, recent advances in the use of ATI ligands for stabilizing heavy analogs of carbon oxo compounds are showcased.

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Section: Reactions With Electrophilesmentioning

confidence: 99%

Section: Ligand Cooperativitymentioning

confidence: 99%

New Perspectives for Aminotroponiminates: Coordination Chemistry, Redox Behavior, Cooperativity, and Catalysis

Hanft

Lichtenberg

2018

Eur J Inorg Chem

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“…13,28,29 Precursor synthesis and characterization Bis(amidinato)germylene 3 was prepared by treatment of Cl 2 Ge·dioxane with the lithium amidinate salt in a 1 : 2 stoichiometry according to the method previously described (Scheme 3). 30 This germanium(II) species was isolated as a pale yellow powder which is stable under an inert atmosphere and can be stored for long periods at low temperature (−30°C).…”

Section: Surface-ligand Composition and Dynamicsmentioning

confidence: 99%

From rational design of organometallic precursors to optimized synthesis of core/shell Ge/GeO₂nanoparticles

et al. 2015

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The synthesis of germanium nanoparticles has been carried out, thanks to the design of novel aminoiminate germanium(II) precursors: (ATI)GeZ (with Z = OMe, NPh2, and ATI = N,N'-diisopropyl-aminotroponiminate) and (Am)2Ge (Am = N,N'-bis(trimethylsilyl)phenyl amidinate). These complexes were fully characterized by spectroscopic techniques as well as single crystal X-ray diffraction. The thermolysis of both complexes yielded NPs which display similar features that are a Ge/GeO2 core/shell structure with a mean diameter close to 5 nm with a narrow size distribution (<15%). Whereas the high temperatures (>300 °C) classically reported in the literature for the preparation of germanium-based NPs were necessary for thermolysis of the complexes (ATI)GeZ, the use of amidinate-based precursors allows the preparation at an unprecedented low temperature (160 °C) for the thermolytic route. As suggested by a mechanistic study, the lower reactivity of (ATI)GeZ (for which the concomitant use of high temperature and acidic reagent is required) was explained in terms of lower ring strain compared to the case of (Am)2Ge.

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“…The In-I and In-N distances (2.67-2.69Å and 2.11-2.12Å respectively) are in the normal range for tricoordinated or tetracoordinated indium compounds. 143,144 Hence, the reactions of the germanium-tungsten complex with MX 3 have not been investigated.…”

Section: Reaction Of L 2 (Cl)gew(co) 5 With Agpfmentioning

confidence: 99%

Three‐coordinate divalent Group 14 element derivatives and related compounds

Saur

Alonso

Barrau

2005

Applied Organom Chemis

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INTRODUCTIONThis paper is an overview of a particular part of our systematic investigation of the divalent germanium and tin species focusing on the use in this chemistry of a β-diketiminato ligand with no encumbering aryl groups on the nitrogen. The bidentate three-atom bridging ligand L 2 (L 2 = PhNC(Me)CHC(Me)NPh), by its remarkable stabilizing properties, allows for easy isolation of subvalent germanium and tin compounds and, as such, permits a general insight on the chemistry of such species. The emphasis here will be on the divalent species L 2 (X)M (M = Ge, Sn), the germanechalcogenones L 2 (Cl)Ge Y, the transition- L (n−x) and the cationic ger- IntroductionThe divalent species of Group 14 elements are the heavier carbene analogues; for recent reviews, see Refs 6-10. They are generally transient species. As a general rule, when these species contain unfunctionalized organic ligands, they undergo rapid oligomerization and polymerization. In the last two decades, two principal methods of stabilization have been particularly investigated. Thus, various kinetically and/or thermodynamically stabilized divalent germanium and tin compounds have been isolated in a monomeric state. 1 -5,11 -81 The use of bulky groups bound to the Group 14 element to prevent aggregation permitted the first syntheses of stable monomer divalent species; the most noticeable are the dialkyl-germylene and -stannylene reported by Lappert and co-workers, 12 the first stable monomeric arylgermylene ((Mes * ) 2 Ge (Mes * = 2,4,6-t Bu 3 -phenyl)) described by Du Mont and co-workers, 14 and the well-known aryl-germylene and -stannylene Tbt(Tip)M 14 (M 14 = Ge, Sn; Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Tip = 2,4,6-i Pr 3 -phenyl) of Okazaki and co-workers. 25,29The ligand backbone may also play an important role in improving stability. Thus, the presence of ligands with donor side arms on the germanium or the tin element can (by transfer of electron density) reduce the deficit on 37 is, to our knowledge, the first example of an intramolecular base stabilized homoleptic dialkylgermylene. Various amino-, phosphino-, thioalkoxy-, alkoxy-and aryloxy-divalent species have also been isolated in monomeric form owing to this method of stabilization; one should mention in particular the studies of Jutzi and co-workers, 28,32,54,71 Veith and coworkers, 15,18,40,66 Parkin and co-workers, 67 Jurkschat and co-workers, 77,78 Dias and co-workers 31,35,42,69,80,81 and Roesky and co-workers. Main Group Metal Compounds -5Although a large number of homoleptic divalent germanium and tin species have been isolated using these concepts of stabilization, there are fewer examples of heteroleptic compounds having been reported, though the first functional heteroleptic germylenes R(Cl)Ge (R = Et, Ph) were obtained as viscous oils in the 1970 by our group.6 Few solidstate structures of such heteroleptic compounds have been described. Noteworthy examples are in the area of thermodynamic stabilization, the acetylacetonatogermylene R(I)Ge (R = OC (Me) 46...

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Cationic Indium Alkyl Complexes Incorporating Aminotroponiminate Ligands

Cited by 43 publications

References 90 publications

New Perspectives for Aminotroponiminates: Coordination Chemistry, Redox Behavior, Cooperativity, and Catalysis

New Perspectives for Aminotroponiminates: Coordination Chemistry, Redox Behavior, Cooperativity, and Catalysis

From rational design of organometallic precursors to optimized synthesis of core/shell Ge/GeO₂nanoparticles

Three‐coordinate divalent Group 14 element derivatives and related compounds

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Cationic Indium Alkyl Complexes Incorporating Aminotroponiminate Ligands

Cited by 43 publications

References 90 publications

New Perspectives for Aminotroponiminates: Coordination Chemistry, Redox Behavior, Cooperativity, and Catalysis

New Perspectives for Aminotroponiminates: Coordination Chemistry, Redox Behavior, Cooperativity, and Catalysis

From rational design of organometallic precursors to optimized synthesis of core/shell Ge/GeO2nanoparticles

Three‐coordinate divalent Group 14 element derivatives and related compounds

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From rational design of organometallic precursors to optimized synthesis of core/shell Ge/GeO₂nanoparticles