Synthesis of a carborane-substituted bis(phosphanido) cobaltate(<scp>i</scp>), ligand substitution, and unusual P<sub>4</sub>fragmentation

Coburger, Peter; Leitl, Julia; Scott, Daniel J.; Hierlmeier, Gabriele; Shenderovich, Ilya G.; Hey‐Hawkins, Evamarie; Wolf, Robert

doi:10.1039/d1sc02948g

Cited by 12 publications

(18 citation statements)

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“…The reaction of 4 a – d with the CN − anion represents a remarkable [3+1] fragmentation of a tetraphosphido ligand to yield a cyclo ‐P 3 − species and an organic monophosphorus compound. While a few transition‐metal‐mediated [3+1] fragmentations of P 4 are known in which the generated P 3 and P 1 moieties remain coordinated to a transition metal atom, [28b,35b,38] the release of P 1 species from polyphosphorus ligands has rarely been observed [3,4,33f,35a,39] …”

Section: Resultsmentioning

confidence: 99%

Cobalt‐Mediated [3+1] Fragmentation of White Phosphorus: Access to Acylcyanophosphanides

Hauer,

Horsley Downie,

Balázs

et al. 2024

Angew Chem Int Ed

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Despite the accessibility of numerous transition metal polyphosphido complexes through transition‐metal‐mediated activation of white phosphorus, the targeted functionalization of Pn ligands to obtain functional monophosphorus species remains challenging. In this study, we introduce a new [3+1] fragmentation procedure for cyclo‐P4 ligands, leading to the discovery of acylcyanophosphanides and ‐phosphanes. Treatment of the complex [K(18c‐6)][(Ar*BIAN)Co(η4‐P4)] ([K(18c‐6)]3, BIAN = 1,2‐bis(arylimino)acenaphthene diimine) with acyl chlorides results in the formation of acylated tetraphosphido complexes [(Ar*BIAN)Co(η4‐P4C(O)R)] (R = tBu, Cy, 1‐Ad, Ph; 4a‐d). Subsequent reaction of 4a‐d with cyanide salts yields acylated cyanophosphanides [RC(O)PCN]− (9a‐d−) and the cyclo‐P3 cobaltate anion [(Ar*BIAN)Co(η3‐P3)(CN)]− (8−). Further reactions of 4a‐d with trimethylsilyl cyanide (Me3SiCN) and isocyanides provide insight into a plausible mechanism of this [3+1] fragmentation reaction, as these reagents partially displace the P4C(O)R ligand from the cobalt center. Several potential intermediates of the [3+1] fragmentation were characterized. Additionally, the introduction of a second acyl substituent was achieved by treating [K(18c‐6)]9b with CyC(O)Cl, resulting in the first bis(acyl)monocyanophosphine (CyC(O))2PCN (10).

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Section: Resultsmentioning

confidence: 99%

Cobalt‐Mediated [3+1] Fragmentation of White Phosphorus: Access to Acylcyanophosphanides

Hauer,

Horsley Downie,

Balázs

et al. 2024

Angew Chem Int Ed

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“…282 Given the limited reaction profile observed for 328, the authors anticipated that an increase in the bulk of the ligand used would allow for the synthesis of heteroleptic complexes that could maintain labile ligands or vacant coordination sites. Thus, the mesityl-substituted diphosphetane rac-329 was treated with cobaltate 239 in the presence of [18]crown-6 (Scheme 41, right) to afford the heteroleptic 134 Similarly, reaction of the diphosphetane rac-329 with the Ni( 0 (rac-332). 282 Complex rac-330 provided a suitable platform to synthesize a variety of bis(phosphanido) complexes by exploitation of the labile η 4 -cod ligand.…”

Section: Metallocene Anionsmentioning

confidence: 99%

“…In contrast, by using a 2:1 rac-330:P 4 ratio and adding [18]crown-6, the reaction product is a bimetallic complex, [K( [18] second equivalent of the bis(phosphanido)cobaltate rac-330. 134 Wolf and co-workers studied the activation of P 4 by a heteroleptic magnesium cobaltate sandwich complex. 427 Treatment of [( Dep nacnac)MgCo(P 2 C 2 tBu 2 )(η 4 -cod)] (688, vide supra) with white phosphorus (P 4 ) in toluene (75 °C, 18 h) led to the formation of the cyclo-P 4 sandwich complex [( Dep nacnac)MgCo(cyclo-P 4 )(P 2 C 2 tBu 2 )] 2 (1073, Scheme 152) via substitution of the 1,5-cyclooctadiene ligand.…”

Section: General Remarks On White Phosphorusmentioning

confidence: 99%

“…282 Complex rac-330 provided a suitable platform to synthesize a variety of bis(phosphanido) complexes by exploitation of the labile η 4 -cod ligand. 134 Treating rac-330 with cyclohexyl isocyanide cleanly substitutes the cyclooctadiene ligand, yielding the bis(isocyanide) complex [K( [18] Scheme 42,top). The characterization of this bis-(isocyanide) complex by multinuclear NMR and FT-IR spectroscopy, elemental analysis, and X-ray diffraction confirmed the substitution of the labile ligand, and indicated that the bis(phosphanido) ligand acts as a strong σ-donor, making the Co(I) center more electron-rich [ν CN (333) = 2029 and 1938 cm −1 (see Table 1) vs ν CN (free ligand) = 2136 cm −1 ].…”

Section: Metallocene Anionsmentioning

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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“…For instance, anionic metal-dinitrogen adducts have been used for the protonation and silylation of dinitrogen to form ammonia and tris(trimethylsilyl)amine, respectively, − and C–CN bond activation has been achieved with rhodium metalates . The activation of small-molecule phosphorus reagents such as P 4 , − phosphaalkynes (RCP), and P–P bonds , has also been demonstrated. Each of these highlighted examples of small-molecule activation is performed with noncarbonyl metalates.…”

Section: Introductionmentioning

confidence: 99%

Applications of Low-Valent Transition Metalates: Development of a Reactive Noncarbonyl Rhenium(I) Anion

et al. 2022

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Conspectus Low-valent transition metalatesanionic, electronic-rich organometallic complexescomprise a class of highly reactive chemical reagents that find integral applications in organic synthesis, small-molecule activation, transient species stabilization, and M–E bond formation, among others. The inherent reactivity of such electron-rich metal centers has necessitated the widespread use of strong backbonding ligands, particularly carbonyls, to aid in the isolation and handling of metalate reagents, albeit sometimes at the expense of partially masking their full reactivity. However, recent synthetic explorations into transition-metalate complexes devoid of archetypic back-bonding ligands have led to the discovery of highly reactive metalates capable of performing a variety of novel chemical transformations. Building on our group’s long-standing interest in reactive organometallic species, a series of rational progressions in early-to-middle transition-metal chemistry ultimately led to our isolation of a rhenium(I) β-diketiminate cyclopentadienide metalate that displays exceptional reactivity. We have found this Re(I) metalate to be capable of small-molecule activation; notably, the complex reversibly binds dinitrogen in solution and can be utilized to trap N2 for the synthesis of functionalized diazenido species. By employing isolobal analogues to N2 (CO and RNC), we were able to thoroughly monitor the mechanism of activation and conclude that the metalate’s sodium counterion plays an integral role in promoting dinitrogen activation through a novel side-on interaction. The Re(I) metalate is also used in forming a variety of M–E bonds, including a series of uncommon rhenium-tetrylene (Si, Ge, and Sn) complexes that display varying degrees of multiple bonding. These metal tetrylenes act to highlight deviations in chemical properties within the group 14 elements. Our metalate’s utility also applies to metal–metal bond formation, as demonstrated through the synthesis of a heterotetrametallic rhenium–zinc dimer. In this reaction, the Re(I) metalate performs a dual role as a reductant and metalloligand to stabilize a transient Zn2 2+ core fragment. Finally, the metalate displays unique reactivity with uranium(III) to yield the first transition metal–actinide inverse-sandwich bonds, in this case with three rhenium fragments bound through their Cp moieties surrounding the uranium center. Notably, throughout these endeavors we demonstrate that the metalate displays reactivity at multiple locations, including directly at the rhenium metal center, at a Cp carbon, through a Cp-sandwich mode, or through reversibly bound dinitrogen. Overall, the rhenium(I) metalate described herein demonstrates utility in diverse applications: small-molecule activation, the stabilization of reduced and/or unstable species, and the formation of unconventional M–E/M–M bonds or heterometallic complexes. Moving forward, we suggest that the continued discovery of noncarbonyl, electron-rich transition-metal anions featuring new or unconve...

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Synthesis of a carborane-substituted bis(phosphanido) cobaltate(i), ligand substitution, and unusual P₄fragmentation

Abstract: Oxidative addition of the P‒P single bond of an ortho-carborane-derived 1,2-diphosphetane (1,2-C2(PMes)2B10H10) (Mes = 2,4,6-Me3C6H2) to cobalt(-I) and nickel(0) sources affords the first heteroleptic complexes of a carborane-bridged bis(phosphanido) ligand....

Cited by 12 publications

References 66 publications

Cobalt‐Mediated [3+1] Fragmentation of White Phosphorus: Access to Acylcyanophosphanides

Cobalt‐Mediated [3+1] Fragmentation of White Phosphorus: Access to Acylcyanophosphanides

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

Applications of Low-Valent Transition Metalates: Development of a Reactive Noncarbonyl Rhenium(I) Anion

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Synthesis of a carborane-substituted bis(phosphanido) cobaltate(i), ligand substitution, and unusual P4fragmentation

Abstract: Oxidative addition of the P‒P single bond of an ortho-carborane-derived 1,2-diphosphetane (1,2-C2(PMes)2B10H10) (Mes = 2,4,6-Me3C6H2) to cobalt(-I) and nickel(0) sources affords the first heteroleptic complexes of a carborane-bridged bis(phosphanido) ligand....

Cited by 12 publications

References 66 publications

Cobalt‐Mediated [3+1] Fragmentation of White Phosphorus: Access to Acylcyanophosphanides

Cobalt‐Mediated [3+1] Fragmentation of White Phosphorus: Access to Acylcyanophosphanides

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

Applications of Low-Valent Transition Metalates: Development of a Reactive Noncarbonyl Rhenium(I) Anion

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Synthesis of a carborane-substituted bis(phosphanido) cobaltate(i), ligand substitution, and unusual P₄fragmentation