The unusual coordination chemistry of phosphorus-rich linear and cyclic oligophosphanide anions

Gómez‐Ruiz, Santiago; Hey‐Hawkins, Evamarie

doi:10.1016/j.ccr.2010.11.020

Cited by 46 publications

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References 101 publications

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“…200 kJ mol À1 in typical compounds), the structural diversity of polyphosphorus derivatives is unrivalled in main group chemistry. [1][2][3][4][5][6] Seminal contributions of Baudler, von Schnering, and many others have unraveled ap lethora of neutral polyphosphanes and polyphosphanide anions, [2][3][4][5] and the coordination behavior of such species has been investigated extensively in the past. [5,6] Tr ansition-metal polyphosphides such as pentamethylpentaphosphaferrocene are used as building blocks for 1D and 2D polymers and spherical supramolecules.…”

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“…[1][2][3][4][5][6] Seminal contributions of Baudler, von Schnering, and many others have unraveled ap lethora of neutral polyphosphanes and polyphosphanide anions, [2][3][4][5] and the coordination behavior of such species has been investigated extensively in the past. [5,6] Tr ansition-metal polyphosphides such as pentamethylpentaphosphaferrocene are used as building blocks for 1D and 2D polymers and spherical supramolecules. [7,8] Alkylation, protonation, halogenation, reduction, and oxidation reactions of polyphosphorus units in neutral transition-metal complexes have been reported, [9] while the reaction of main-group-element nucleophiles such as amides,p hosphanides,h ydrocarbyl anions,a nd N-heterocyclic carbenes (NHCs) is av ersatile route to anionic complexes with functionalized polyphosphido ligands.…”

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“…As for 1-iPr,adetailed spectroscopic characterization of 1-iPr·GaCl 3 was hampered by its rapid decomposition in solution. In contrast, however, the mesityl-substituted derivative 1-Mes can be synthesized by an analogous procedure using K[Cp Ar ]a nd [P 5 Mes 2 ]-[GaCl 4 ](Scheme 1b). 1-Mes is significantly more stable than 1-iPr (see Figure S87 for a 31 P{ 1 H} NMR monitoring study of its decomposition).…”

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Functionalization of Pentaphosphorus Cations by Complexation

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The chemistry of polyphosphorus cations has rapidly developed in recent years, but their coordination behavior has remained mostly unexplored. Herein, we describe the reactivity of [P5R2]+ cations with cyclopentadienyl metal complexes. The reaction of [CpArFe(μ‐Br)]2 (CpAr=C5(C6H4‐4‐Et)5) with [P5R2][GaCl4] (R=iPr and 2,4,6‐Me3C6H2 (Mes)) afforded bicyclo[1.1.0]pentaphosphanes (1‐R, R=iPr and Mes), showing an unsymmetric “butterfly” structure. The same products 1‐R were formed from K[CpAr] and [P5R2][GaCl4]. The cationic complexes [CpArCo(η4‐P5R2)][GaCl4] (2‐R[GaCl4], R=iPr and Cy) and [(CpArNi)2(η3:3‐P5R2)][GaCl4] (3‐R[GaCl4]) were obtained from [P5R2][GaCl4] and [CpArM(μ‐Br)]2 (M=Co and Ni) as well as by using low‐valent “CpArMI” sources. Anion metathesis of 2‐R[GaCl4] and 3‐R[GaCl4] was achieved with Na[BArF24]. The P5 framework of the resulting salts 2‐R[BArF24] can be further functionalized with nucleophiles. Thus reactions with [Et4N]X (X=CN and Cl) give unprecedented cyano‐ and chloro‐functionalized complexes, while organo‐functionalization was achieved with CyMgCl.

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Functionalization of Pentaphosphorus Cations by Complexation

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“…[21,22] Although their reactivity with elemental sulfur,s elenium, and N-heterocyclic carbenes has been studied, [23,24] their coordination behavior is completely unknown. Herein, we describe reactions of cyclopentadienyl iron, cobalt, and nickel complexes with such cations,w hich result in the formation of neutral bicyclo-[1.1.0]pentaphosphanes 1-R (R = iPr and Mes) and cationic P 5 R 2 complexes [(Cp Ar Co)(h 4 -P 5 R 2 )] + ([2-R] + ;C p Ar = C 5 (C 6 H 4 -4-Et) 5 ,R = iPr and Cy) and [(Cp Ar Ni) 2 (h 3:3 -P 5 R 2 )] ([3-R] + ). Unusual (pseudo)halogen and organo-substituted P 5 R 2 X( X= Cl, CN,a nd Cy) frameworks are the result of post-functionalization reactions of [2-R] + with [Et 4 N][X] (X = CN and Cl) and the Grignard reagent CyMgCl.…”

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Functionalization of Pentaphosphorus Cations by Complexation

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The chemistry of polyphosphorus cations has rapidly developed in recent years,b ut their coordination behavior has remained mostly unexplored. Herein, we describe the reactivity of [P 5 R 2 ] + cations with cyclopentadienyl metal complexes.T he reaction of [Cp Ar Fe(m-Br)] 2 (Cp Ar = C 5 (C 6 H 4 -4-Et) 5 )with [P 5 R 2 ][GaCl 4 ](R= iPr and 2,4,6-Me 3 C 6 H 2 (Mes)) afforded bicyclo[1.1.0]pentaphosphanes (1-R,R = iPr and Mes), showing an unsymmetric "butterfly" structure.The same products 1-R were formed from K[Cp Ar ]a nd [P 5 R 2 ][GaCl 4 ]. The cationic complexes [Cp Ar Co(h 4 -P 5 R 2 )][GaCl 4 ]( 2-R-[GaCl 4 ], R= iPr and Cy) and [(Cp Ar Ni) 2 (h 3:3 -P 5 R 2 )][GaCl 4 ] (3-R[GaCl 4 ]) were obtained from [P 5 R 2 ][GaCl 4 ]and [Cp Ar M-(m-Br)] 2 (M = Co and Ni)a sw ell as by using low-valent "Cp Ar M I "s ources.A nion metathesis of 2-R[GaCl 4 ]a nd 3-R[GaCl 4 ]w as achieved with Na[BArF 24 ]. The P 5 framework of the resulting salts 2-R[BArF 24 ]c an be further functionalizedwith nucleophiles.Thus reactions with [Et 4 N]X (X = CN and Cl) give unprecedented cyano-and chlorofunctionalizedcomplexes,while organo-functionalizationw as achieved with CyMgCl.

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Low‐Oxidation‐State Main Group CompoundsUpdate based on the original article by Charles L. B. Macdonald and Bobby D. Ellis,Encyclopedia of Inorganic ChemistrySecond Edition, © 2005, John Wiley & Sons, Ltd.

Macdonald

Ellis

Swidan

2012

Encyclopedia of Inorganic and Bioinorganic Chemistry

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The synthesis and chemistry of compounds containing groups 1, 2, and 13‐15 elements in unusually low oxidation states or valence states is presented. In general, the oxidation or valence state of an element influences the chemistry of the compounds in which the atom is found. For the main group elements, compounds containing elements in lower‐than‐usual oxidation or valence states exhibit significantly different structural features, modes of bonding, and chemistry than is observed for compounds containing the element in a more typical oxidation state. The elements of the s‐block form a limited number of low‐oxidation‐state compounds and the elements of groups 16‐18 are generally found in the lowest available oxidation state. Thus, this article provides an overview of the following classes of low‐valent main group species: the chemistry of group 2 elements in the +1 oxidation state, the chemistry of group 13 elements in oxidation states lower than +3, the chemistry of group 14 elements in oxidation states lower than +2, and the chemistry of the group 15 elements in oxidation states lower than +3. Numerous exemplary modes of reactivity are presented, and the utility of some low‐oxidation‐state compounds as catalysts or precursors to materials is acknowledged.

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The unusual coordination chemistry of phosphorus-rich linear and cyclic oligophosphanide anions

Cited by 46 publications

References 101 publications

Functionalization of Pentaphosphorus Cations by Complexation

Functionalization of Pentaphosphorus Cations by Complexation

Functionalization of Pentaphosphorus Cations by Complexation

Low‐Oxidation‐State Main Group CompoundsUpdate based on the original article by Charles L. B. Macdonald and Bobby D. Ellis,Encyclopedia of Inorganic ChemistrySecond Edition, © 2005, John Wiley & Sons, Ltd.

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