Hydrazidokomplexe früher Übergangsmetalle: maskierte Metallanitrene durch Spaltung von N‐N‐Bindungen

Mindiola, Daniel J.

doi:10.1002/ange.200704987

Cited by 18 publications

(3 citation statements)

References 44 publications

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“…As evidenced by the formation of the uranyl complex 8, the PNP ligand is able to support U VI and efforts are now directed towards exploiting systems such as 4 as entries to actinide metallanitrene and nitride chemistry. [19] Received: December 15, 2008 Published online: February 16,2009 . Keywords: actinides · hydrazonido compounds · metallocenes · N,P ligands · uranium…”

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confidence: 99%

Challenging the Metallocene Dominance in Actinide Chemistry with a Soft PNP Pincer Ligand: New Uranium Structures and Reactivity Patterns

et al. 2009

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A soft embrace for U: Replacement of C(5)Me(5) by the soft PNP pincer ligand is a successful strategy to promote new reactivities and support new structures for the actinide series (see picture, py-O = pyridine-N-oxide). The specific electronic and steric properties of the PNP ligand enable access to previously unreported structures not available for the C(5)Me(5) ligand set and support not only low-valent uranium but also the high-valent uranium(VI) ion.

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confidence: 99%

Challenging the Metallocene Dominance in Actinide Chemistry with a Soft PNP Pincer Ligand: New Uranium Structures and Reactivity Patterns

et al. 2009

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“…Furthermore, they can be used as catalysts for hydrohydrazination reactions and, as shown in recent studies, in activation reactions of hydride bonds of silanes and boranes . Especially the (reductive) cleavage of the N α –N β bond is of interest in these kinds of reactions, which offers completely new synthetic routes in contrast to the titanium imido complexes . Titanium hydrazido complexes are usually synthesized by ligand exchange reactions of titanium imido complexes with the corresponding hydrazines (Scheme ).…”

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confidence: 99%

Direct Access to Terminal Titanocene Hydrazides via Bis(η⁵:η¹-pentafulvene)titanium Complexes and 1,1-Diphenylhydrazine

et al. 2018

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The formation of the titanocene hydrazido complex 2 via double N−H bond activations at ambient temperature of 1,1-diphenylhydrazine by the use of bis(η 5 :η 1adamantylidenepentafulvene)titanium complex 1 have been investigated. Starting from the titanium hydrazido complex 2, [2 + 2] cycloaddition and bond activation reactions are realized. In reaction with carbodiimides, the asymmetric N,N-bound ureato(2−) product 3 is observed. By use of nitriles, in addition to the [2 + 2] cycloaddition, the insertion of a second equivalent of the nitrile into the Ti−N bond is found (4). By reaction of 2 with carbon disulfide the symmetric S,S-bound thioureato(2−) complex 5 is isolated, whereas in reaction with carbon monoxide the cleavage of the N−N bond of the hydrazide unit is observed, resulting in the formation of the titanocene monocyanate 6. In contrast to the [2 + 2] cycloaddition reactions, for sterically demanding boranes such as 9-borabicyclo[3.3.1]nonane and catecholborane the hydroboration of the TiN double bond is observed, leading to the titanocene hydride complex 7 and the titanium(III) cation 8.

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“…Thec ombined characterization data for complexes 3-5 reveal that the S-K interaction is conserved in both solution and the solid state.H owever,p reliminary reactivity data suggest that the S-K interaction is quite labile,p ermitting these complexes to behave as "masked" terminal sulfides. [38] Fore xample,e xposure of complex 4 to an atmosphere of nitrous oxide (N 2 O) resulted in ar apid color change from (8) 170.08 (5) . .…”

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Synthesis of a “Masked” Terminal Nickel(II) Sulfide by Reductive Deprotection and its Reaction with Nitrous Oxide

Hartmann

Hayton

2015

Angewandte Chemie

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The addition of 1 equiv of KSCPh3 to [LRNiCl] (LR={(2,6‐iPr2C6H3)NC(R)}2CH; R=Me, tBu) in C6H6 results in the formation of [LRNi(SCPh3)] (1: R=Me; 2: R=tBu) in good yields. Subsequent reduction of 1 and 2 with 2 equiv of KC8 in cold (−25 °C) Et2O in the presence of 2 equiv of 18‐crown‐6 results in the formation of “masked” terminal NiII sulfides, [K(18‐crown‐6)][LRNi(S)] (3: R=Me; 4: R=tBu), also in good yields. An X‐ray crystallographic analysis of these complexes suggests that they feature partial multiple‐bond character in their NiS linkages. Addition of N2O to a toluene solution of 4 provides [K(18‐crown‐6)][LtBuNi(SNNO)], which features the first example of a thiohyponitrite (κ2‐[SNNO]2−) ligand.

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Hydrazidokomplexe früher Übergangsmetalle: maskierte Metallanitrene durch Spaltung von N‐N‐Bindungen

Cited by 18 publications

References 44 publications

Challenging the Metallocene Dominance in Actinide Chemistry with a Soft PNP Pincer Ligand: New Uranium Structures and Reactivity Patterns

Challenging the Metallocene Dominance in Actinide Chemistry with a Soft PNP Pincer Ligand: New Uranium Structures and Reactivity Patterns

Direct Access to Terminal Titanocene Hydrazides via Bis(η⁵:η¹-pentafulvene)titanium Complexes and 1,1-Diphenylhydrazine

Synthesis of a “Masked” Terminal Nickel(II) Sulfide by Reductive Deprotection and its Reaction with Nitrous Oxide

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Hydrazidokomplexe früher Übergangsmetalle: maskierte Metallanitrene durch Spaltung von N‐N‐Bindungen

Cited by 18 publications

References 44 publications

Challenging the Metallocene Dominance in Actinide Chemistry with a Soft PNP Pincer Ligand: New Uranium Structures and Reactivity Patterns

Challenging the Metallocene Dominance in Actinide Chemistry with a Soft PNP Pincer Ligand: New Uranium Structures and Reactivity Patterns

Direct Access to Terminal Titanocene Hydrazides via Bis(η5:η1-pentafulvene)titanium Complexes and 1,1-Diphenylhydrazine

Synthesis of a “Masked” Terminal Nickel(II) Sulfide by Reductive Deprotection and its Reaction with Nitrous Oxide

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Direct Access to Terminal Titanocene Hydrazides via Bis(η⁵:η¹-pentafulvene)titanium Complexes and 1,1-Diphenylhydrazine