Synthesis of 1,3-Dimetallo-1,3-diphosphetane-2,4-diones. X-ray Structure Analysis of Cp*(CO)2FeP[Cr(CO)5]C(O)P[Fe(CO)2Cp*]C(O) (Cp* = η5-C5Me5)

Weber, Lothar; Torwiehe, Bärbel; Bassmann, Gyn; Stammler, Hans‐Georg; Neumann, Beate

doi:10.1021/om9505470

Cited by 40 publications

(25 citation statements)

References 22 publications

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“…[68] Thef our-membered 1,3-diphosphetane-2,4-dione core of such molecules is the result of ah ead-to-tail cyclization of two P = Cb onds.T he formation of this type of dimer is characteristic for phosphaketenes,a nd this Woodward-Hoffmann allowed [2p s + 2p a ]d imerization has been shown to follow asynchronous concerted mechanism. [68] Thef our-membered 1,3-diphosphetane-2,4-dione core of such molecules is the result of ah ead-to-tail cyclization of two P = Cb onds.T he formation of this type of dimer is characteristic for phosphaketenes,a nd this Woodward-Hoffmann allowed [2p s + 2p a ]d imerization has been shown to follow asynchronous concerted mechanism.…”

Section: Four-membered Heterocyclesmentioning

confidence: 99%

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: Four-membered Heterocyclesmentioning

confidence: 99%

The Chemistry of the 2‐Phosphaethynolate Anion

2018

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“…Further attempts to prepare [M]PCO or [M]OCP complexes by reaction of carbonyl complexes with NaPH 2 failed so far, and transition‐metal complexes of terminal PCO − anions remain unknown. The reaction of cyclopentadienyliron(II) bromide complexes with Li(OCP) has been investigated and may proceed through [Fe]PCO intermediates, but only a dimer with a central 1,3‐diphosphetane‐2,4‐dione ring was isolated in low yield 9. The stability and electronic properties10 of the PCO − ion and some ion pairs with alkali metals have been computed.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Terminal [Re(XCO)(CO)₂(triphos)] (X=N, P): Isocyanate versus Phosphaethynolate Complexes

Alidori

Heift

Santiso‐Quiñones

et al. 2012

Chemistry A European J

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The terminal rhenium(I) phosphaethynolate complex [Re(PCO)(CO)(2)(triphos)] has been prepared in a salt metathesis reaction from Na(OCP) and [Re(OTf)(CO)(2)(triphos)]. The analogous isocyanato complex [Re(NCO)(CO)(2)(triphos)] has been likewise prepared for comparison. The structure of both complexes was elucidated by X-ray diffraction studies. While the isocyanato complex is linear, the phosphaethynolate complex is strongly bent around the pnictogen center. Computations including natural bond orbital (NBO) theory, natural resonance theory (NRT), and natural population analysis (NPA) indicate that the isocyanato complex can be viewed as a classic Werner-type complex, that is, with an electrostatic interaction between the Re(I) and the NCO group. The phosphaethynolate complex [Re(P=C=O)(CO)(2)(triphos)] is best described as a metallaphosphaketene with a Re(I)-phosphorus bond of highly covalent character.

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“…Noch weniger Informationen liegen u È ber stabile acyclische Stibaalkene R 1 ±Sb=CR 2 2 vor, die sich im wesentlichen auf Moleku È le wie Me 3 SiOC(R)=Sb±Sb=C(R)OSiMe 3 (R = Mes, Mes*) und Mes*C(O)Sb=C(Mes*)OH beschra È nken [7,8]. (1)) [9]. (1)) [9].…”

Section: Introductionunclassified

Synthese und Struktur von η1-Phosphaallyl-, η1-Arsaallylund η1-Stibaallyleisen-Komplexen [(η5-C5Me5)(CO)2Fe–E(SiMe3)C(OSiMe3)=CPh2] (E = P, As, Sb)

Weber

Uthmann

Kleinebekel

et al. 2000

Z. anorg. allg. Chem.

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Inhaltsu È bersicht. Bei der Umsetzung a Èquimolarer Mengen an [(g 5 -C 5 Me 5 )(CO) 2 FeE(SiMe 3 ) 2 ] (1 a: E = P; 1 b: As; 1 c: Sb) mit Diphenylketen werden die g 1 -Phosphaallyl-, g 1 -Arsaallylund g 1 -Stibaallylkomplexe [(g 5 -C 5 Me 5 )(CO) 2 Fe±E(SiMe 3 )-C(OSiMe 3 )=CPh 2 ] (2 a: E = P; 2 b: As; 2 c: Sb) erhalten. Die Moleku È lstukturen von 2 b und 2 c wurden durch Ro È ntgenstrukturanalysen ermittelt.Syntheses and Structures of g 1 -Phosphaallyl, g 1 -Arsaallyl, and g 1 -Stibaallyl Iron Complexes [(g 5 -C 5 Me 5 )(CO) 2 Fe±E(SiMe 3 )C(OSiMe 3 )=CPh 2 ] (E = P, As, Sb)Abstract. The reaction of equimolar amounts of [(g 5 -C 5 Me 5 )(CO) 2 Fe±E(SiMe 3 ) 2 ] (1 a: E = P; 1 b: As; 1 c: Sb) and diphenylketene afforded the g 1 -phosphaallyl-, g 1 -arsaallyl-, and g 1 -stibaallyl complexes [(g 5 -C 5 Me 5 )(CO) 2 Fe±E(SiMe 3 )-C(OSiMe 3 )=CPh 2 ] (2 a: E = P; 2 b: As; 2 c: Sb). The molecu-lar structures of 2 b and 2 c were elucidated by single crystal X-ray analyses.

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Synthesis of 1,3-Dimetallo-1,3-diphosphetane-2,4-diones. X-ray Structure Analysis of Cp(CO)₂FeP[Cr(CO)₅]C(O)P[Fe(CO)₂Cp]C(O) (Cp* = η⁵-C₅Me₅)

Cited by 40 publications

References 22 publications

The Chemistry of the 2‐Phosphaethynolate Anion

The Chemistry of the 2‐Phosphaethynolate Anion

Synthesis and Characterization of Terminal [Re(XCO)(CO)₂(triphos)] (X=N, P): Isocyanate versus Phosphaethynolate Complexes

Synthese und Struktur von η1-Phosphaallyl-, η1-Arsaallylund η1-Stibaallyleisen-Komplexen [(η5-C5Me5)(CO)2Fe–E(SiMe3)C(OSiMe3)=CPh2] (E = P, As, Sb)

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Synthesis of 1,3-Dimetallo-1,3-diphosphetane-2,4-diones. X-ray Structure Analysis of Cp*(CO)2FeP[Cr(CO)5]C(O)P[Fe(CO)2Cp*]C(O) (Cp* = η5-C5Me5)

Cited by 40 publications

References 22 publications

The Chemistry of the 2‐Phosphaethynolate Anion

The Chemistry of the 2‐Phosphaethynolate Anion

Synthesis and Characterization of Terminal [Re(XCO)(CO)2(triphos)] (X=N, P): Isocyanate versus Phosphaethynolate Complexes

Synthese und Struktur von η1-Phosphaallyl-, η1-Arsaallylund η1-Stibaallyleisen-Komplexen [(η5-C5Me5)(CO)2Fe–E(SiMe3)C(OSiMe3)=CPh2] (E = P, As, Sb)

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Synthesis of 1,3-Dimetallo-1,3-diphosphetane-2,4-diones. X-ray Structure Analysis of Cp(CO)₂FeP[Cr(CO)₅]C(O)P[Fe(CO)₂Cp]C(O) (Cp* = η⁵-C₅Me₅)

Synthesis and Characterization of Terminal [Re(XCO)(CO)₂(triphos)] (X=N, P): Isocyanate versus Phosphaethynolate Complexes