A Stable Heterocyclic Amino(phosphanylidene‐σ<sup>4</sup>‐phosphorane) Germylene

Rio, Natalia Del; Baceiredo, Antoine; Saffon‐Merceron, Nathalie; Hashizume, Daisuke; Lutters, Dennis; Müller, Thomas; Kato, Tsuyoshi

doi:10.1002/anie.201511956

Cited by 95 publications

(39 citation statements)

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“…[41][42][43][44] As starting materials,G e II halides like those shown in Scheme 8 are suitable.Reactions with Na(OCP) or Na(OCAs) give first the corresponding germanyl substituted phospha-or arsaketenes.These germyl substituted phosphaketenes,R 3 Ge À PCO, are the more stable isomers when compared to derivatives with aG e ÀOÀCXu nit (X = P, As;s ee above). [41][42][43][44] As starting materials,G e II halides like those shown in Scheme 8 are suitable.Reactions with Na(OCP) or Na(OCAs) give first the corresponding germanyl substituted phospha-or arsaketenes.These germyl substituted phosphaketenes,R 3 Ge À PCO, are the more stable isomers when compared to derivatives with aG e ÀOÀCXu nit (X = P, As;s ee above).…”

Section: Angewandte Chemiementioning

confidence: 99%

“…TheG e II -XCO (X = P, As) compounds can be isolated but the arsaketene derivatives are significantly more labile and lose CO at room temperature.T he CO group in these can also be easily replaced by other neutral two-electron donor groups such as PPh 3 or N-heteocyclic carbenes (NHC). [41] A special case is the rearrangement of the diketiminato stabilized germaalkyne with bulky substituents Ar and R that loses an iminyl radical, ArN=CRC,a nd forms compound [DippNC( t Bu)CÀ(H)PGe] 2 in high yield. In all cases,nostable compound with aGe PorGe As could be prepared.…”

Section: Angewandte Chemiementioning

confidence: 99%

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The Chemistry of the 2‐Phosphaethynolate Anion

2018

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In all likelihood the first synthesis of the phosphaethynolate anion, PCO , was performed in 1894 when NaPH was reacted with CO in an attempt to make Na(CP) accompanied by elimination of water. This reaction was repeated 117 years later when it was discovered that Na(OCP) and H are the products of this remarkable transformation. Li(OCP) was synthesized and fully characterized in 1992 but this salt proved to be too unstable to allow for a detailed investigation of its chemistry. It was not until the heavier analogues of this lithium salt were isolated, Na(OCP) and K(OCP) (both of which are remarkably stable and can be even dissolved in water), that the chemistry of this new functional group could be explored. Here we review the chemistry of the 2-phosphaethynolate anion, a heavier phosphorus-containing analogue of the cyanate anion, and describe the wide breadth of chemical transformations for which it has been thus far employed. Its use as a ligand, in decarbonylative and deoxygenative processes, and as a building block for novel heterocycles is described. In the mere twenty-six years since Becker first reported the isolation of this remarkable anion, it has become a fascinating reagent for the synthesis of a vast library of, often unprecedented, molecules and compounds.

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Section: Angewandte Chemiementioning

confidence: 99%

Section: Angewandte Chemiementioning

confidence: 99%

The Chemistry of the 2‐Phosphaethynolate Anion

2018

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“…Recently, we reported the synthesis of a stable N,P‐heterocyclic germylene 1 , which presents an enhanced reactivity compared to classical N‐heterocyclic germylenes because of the peculiar influence of the phosphanylidene–phosphorane moiety . Of particular interest—besides the divalent germylene center—derivative 1 presents two more reactive sites: a weak Ge=P‐π‐bond and a nucleophilic phosphorus center.…”

Section: Figurementioning

confidence: 99%

“…These results suggest that the π‐electron donation of the phosphanylidene–phosphorane fragment to the electron‐deficient germylene center is much stronger than that of the amino group. Similar structural patterns were already observed for 1 , and the Ge−N1 and Ge−P1 bond shortening in 2 (1.918(4) and 2.247(2) Å, respectively in 1 ) is attributed to the stabilization of the germanium lone pair upon coordination to borane and the reduction of the related Pauli repulsion. Indeed, the N1−Ge−P1 angle becomes significantly wider in 2 (115.2(1)° vs. 107.0(2)° in 1 ).…”

Section: Figurementioning

confidence: 99%

“…This result clearly demonstrates that the germylene/borane complex 2 can successively activate two molecules of silane. The enhanced reactivity of cationic germylenes 3 , compared to that of the non‐activated N,P‐germylene 1 , is demonstrated by the almost immediate reaction at room temperature of 3 b with 2,3‐dimethylbutadiene to give the corresponding [4+1] cycloadduct 5 b ; in the case of 1 the reaction needs 3 h to complete (Scheme ) …”

Section: Figurementioning

confidence: 99%

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N,P‐Heterocyclic Germylene/B(C₆F₅)₃ Adducts: A Lewis Pair with Multi‐reactive Sites

et al. 2016

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An N,P-heterocyclic germylene/B(C F ) Lewis adduct 2 presenting multi-reactive sites (P/B Lewis pair, germylene, Ge=P π-bond) is reported. In contrast to classical frustrated Lewis pairs or divalent Group 14 element species, 2 is able to activate two small molecules simultaneously. Of particular interest, 2 reacts with silanes leading to the formation of original cationic germylenes 3, and can be used as a metal-free catalyst for selective CO -hydrosilylation to H C(OSiEt ) .

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