Iron‐Gallium and Cobalt‐Gallium Tetraphosphido Complexes

Ziegler, Christoph G. P.; Hennersdorf, Felix; Weigand, Jan J.; Wolf, Robert

doi:10.1002/zaac.201900351

Cited by 4 publications

(4 citation statements)

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“…Heterobimetallic complexes with highly reduced P 4 ligands, derived from iron and cobalt metalates, were reported in 2020 by Wolf, Weigand and co-workers . The metalates [M(η 4 -C 14 H 10 ) 2 ] − [M = Fe ( 52 ); Co ( 14 )] reacted with the gallium tetraphosphido species [(nacnac)Ga(κ 2 -P 4 )] ( 1049 , nacnac = CH[CMeN(2,6- i Pr 2 C 6 H 3 )] 2 ), which contains an activated (butterfly) P 4 unit .…”

Section: Metalates In Small-molecule Activation and Catalysismentioning

confidence: 99%

“…Magnetic measurements (Evans method and SQUID) indicated that 1064 is a mixed-valent Co I −Co II species, while in 1065 the cyclo-P 3 3− unit bridges two Co(II) centers. 635 386,632 This procedure afforded the heterodinuclear cobalt−gallium compounds [K(dme) 2 {( Ar BIAN)Co(μ-η 4 :κ 2 -P 4 )Ga(nacnac)}] [ Ar BIAN = Dipp BIAN (1069), Mes BIAN (bis(mesitylimino)acenaphthenediimine) (1070)], featuring catena-P 4 ligands. Reactivity studies performed on 1070 showed that these complexes can be functionalized with alkylchlorophosphanes (R n PCl 3−n ) to afford polyphosphorus cyclo-P 5 R 2 compounds.…”

Section: General Remarks On White Phosphorusmentioning

confidence: 99%

“…Heterobimetallic complexes with highly reduced P 4 ligands, derived from iron and cobalt metalates, were reported in 2020 by Wolf, Weigand and co-workers. 632 The metalates [M(η 4 -C 14 H 10 ) 2 ] − [M = Fe (52); Co (14)] reacted with the gallium tetraphosphido species [(nacnac)Ga(κ 2 -P 4 )] (1049, nacnac = CH[CMeN(2,6-iPr 2 C 6 H 3 )] 2 ), which contains an activated (butterfly) P 4 unit. 633 The strategy afforded the heterobimetallic complexes [(η 4 -C 14 Notably, an early, related example of reaction between a ferrate complex and white phosphorus was reported for the heteroleptic metalate [K( [18]crown-6){Cp*Fe(η 4 -C 10 H 8 )}] (201).…”

Section: General Remarks On White Phosphorusmentioning

confidence: 99%

“…The complexes [K(OEt 2 ){Co( Ar BIAN)(η 4 -1,5-cod)}] [ Ar BIAN = Dipp BIAN ( 540 ), Mes BIAN ( 541 )] were treated with [(nacnac)Ga(κ 2 -P 4 )] ( 1049 ) by a synthetic protocol similar to that which yielded [(η 4 -C 14 H 10 )M(μ-η 4 :κ 2 -P 4 )Ga(nacnac)] − [M = Fe ( 1050 ), Co ( 1051 ); Figure , vide supra ]. , This procedure afforded the heterodinuclear cobalt–gallium compounds [K(dme) 2 {( Ar BIAN)Co(μ-η 4 :κ 2 -P 4 )Ga(nacnac)}] [ Ar BIAN = Dipp BIAN ( 1069 ), Mes BIAN (bis(mesitylimino)acenaphthenediimine) ( 1070 )], featuring catena -P 4 ligands. Reactivity studies performed on 1070 showed that these complexes can be functionalized with alkylchlorophosphanes (R n PCl 3– n ) to afford polyphosphorus cyclo -P 5 R 2 compounds.…”

Section: Metalates In Small-molecule Activation and Catalysismentioning

confidence: 99%

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Low-Valent Transition Metalate Anions in Synthesis, Small Molecule Activation, and Catalysis

Landaeta,

Horsley Downie,

Wolf

2024

Chem. Rev.

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This review surveys the synthesis and reactivity of low-oxidation state metalate anions of the d-block elements, with an emphasis on contributions reported between 2006 and 2022. Although the field has a long and rich history, the chemistry of transition metalate anions has been greatly enhanced in the last 15 years by the application of advanced concepts in complex synthesis and ligand design. In recent years, the potential of highly reactive metalate complexes in the fields of small molecule activation and homogeneous catalysis has become increasingly evident. Consequently, exciting applications in small molecule activation have been developed, including in catalytic transformations. This article intends to guide the reader through the fascinating world of low-valent transition metalates. The first part of the review describes the synthesis and reactivity of d-block metalates stabilized by an assortment of ligand frameworks, including carbonyls, isocyanides, alkenes and polyarenes, phosphines and phosphorus heterocycles, amides, and redox-active nitrogen-based ligands. Thereby, the reader will be familiarized with the impact of different ligand types on the physical and chemical properties of metalates. In addition, ion-pairing interactions and metal−metal bonding may have a dramatic influence on metalate structures and reactivities. The complex ramifications of these effects are examined in a separate section. The second part of the review is devoted to the reactivity of the metalates toward small inorganic molecules such as H 2 , N 2 , CO, CO 2 , P 4 and related species. It is shown that the use of highly electron-rich and reactive metalates in small molecule activation translates into impressive catalytic properties in the hydrogenation of organic molecules and the reduction of N 2 , CO, and CO 2 . The results discussed in this review illustrate that the potential of transition metalate anions is increasingly being tapped for challenging catalytic processes with relevance to organic synthesis and energy conversion. Therefore, it is hoped that this review will serve as a useful resource to inspire further developments in this dynamic research field.

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Section: Metalates In Small-molecule Activation and Catalysismentioning

confidence: 99%