Insertion of sodium phosphaethynolate, Na[OCP], into a zirconium–benzyne complex

Kieser, Jerod M.; Gilliard, Robert J.; Rheingold, Arnold L.; Protasiewicz, John D.

doi:10.1039/c7cc01482a

Cited by 20 publications

(18 citation statements)

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“…While this mode of reactivity is the predominant route observed thus far,r ecently additional examples of reactions giving rise to five-membered ring systems have been reported that differ in their mode of reactivity.I n2 017 Grützmacher and Protasiewicz reported on the reaction of az irconiumbenzyne complex [Cp 2 Zr(PMe 3 )(C 6 H 4 )] with OCP À . [80] While the authors originally postulated that such reactions might give rise to 1,3-benzoxaphospholes via af ormal [2+ +3] cycloaddition reaction of the benzyene CCbond with OCP À ,they instead observed the formation of an unusual solid-state coordination polymer consisting of [Cp 2 Zr{k-C, k 2 -P-C 6 H 4 C-(O)P}] 2À dimers bridged by [Na(THF) 2 ] + cations,w hich results from the formal insertion of the P Cb ond of OCP À into one of the ZrÀCb onds of the precursor (Scheme 34). This species can be silylated using trimethylsilyl chloride to afford abimetallic compound exhibiting asingle resonance in its 31 PNMR spectrum at 194.0 ppm.…”

Section: Five-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: Five-membered Heterocyclesmentioning

confidence: 99%

The Chemistry of the 2‐Phosphaethynolate Anion

2018

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“…Insertion of the (OCP)‐anion into a metal–carbon bond was discovered in the reaction of 2b with zirconiumbenzyne complex 251 . Stirring the dark red mixture in THF for 24 h at 25 °C led to the precipitation of bright red 252 in 43 % yield (Scheme ) …”

Section: Reactivity Of 2‐phosphaethynolatesmentioning

confidence: 99%

2‐Phospha‐ and 2‐Arsaethynolates – Versatile Building Blocks in Modern Synthetic Chemistry

Weber

2018

Eur J Inorg Chem

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2-Phosphaethynolates, particularly the sodium salts, Na(OCP), are exceedingly versatile nucleophiles, which renders these species important as precursors to phosphorus-containing π-conjugated heterocycles. Moreover, the 2-phosphaethynolate anion serves as a potent phosphide transfer reagent giving rise to the first stable phosphinidine among other prod-[a] Centrum für Molekulare Materialien, 2176 Scheme 3. Synthesis of [Na(dme) 2 (PCO)] 2 (2a) from 3by bond metathesis.philicity of carbon monoxide is considerably increased by ligation to the iron center, and where 2b was observed as the only P-containing product. [7] In keeping with this, heating a DMF solution of K 3 P 7 and [18]-crown-6 to 150°C under an atmosphere of CO led to the formation of [K([18]-crown-6)](PCO) 5 in addition to polyphosphides K 2 P 16 and K 3 P 21 . Aqueous work up allowed the isolation of 5 as a colorless solid in 38 % yield (Scheme 4). [9] Scheme 4. Synthesis of 5. Alkali Earth Metal 2-PhosphaethynolatesAttempts to emulate Becker's protocol for [Li(dme) 2 ](PCO) with alkaline earth metals was largely met with failure. Exposure of M[P(SiMe 3 ) 2 ] 2 to dimethyl carbonate in THF or DME afforded the corresponding magnesium (6), calcium (7), strontium (8) and barium (9) bis(2-phosphaethynolates), which slowly decomposed in the ethereal solvent. Rapid deterioration of the products was observed in hydrocarbon solvents or by removal of coordinating solvent molecules in vacuo.Solely in the case of the calcium derivative 7, where three DME ligands obviously imparted sufficient stability to the crystals full structural characterization was possible. Otherwise, identification of compounds 6-9 was restricted to NMR evidence (Scheme 5). [6d] Notably, combination of Sr[P(SiMe 3 ) 2 ] 2 with an excess of dimethyl carbonate yielded a few crystals of dinuclear 10, as confirmed by X-ray techniques. [6d] Eur. 2187 Scheme 32. Alkylation reactions of dianion 55 with 2-iodopropane and 4,4′,4′′-trimethoxyphenylmethyl chloride. Scheme 33. Preparation of Li(PCS) (58). 2193 Scheme 49. Synthesis of 98 from 99 and P(SiMe 3 ) 3 . Scheme 50. Synthesis of 98 from Na(OCP) or P 7 (SiMe 3 ) 3 . Scheme 51. Proposed mechanism for the formation of phosphaalkene 98′ from 101′ and (PCO) -(R = Me). Scheme 73. Synthesis of 145 {[K] + = [K{18}-crown-6] + }. 2201 Scheme 79. Synthesis of 153a and 154a. Scheme 80. Synthesis of 153b. Scheme 81. Preparation of 155 and 156 by deprotonation of 152c. Eur. J. Inorg. Chem. 2018, 2175-2227 www.eurjic.org Scheme 95. Formation of adducts 192a-e. Scheme 96. Reaction of 168 with N-heterocyclic carbenes 96 and 193b,c.

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“…3 Natural Resonance Theory calculations have shown that (OCP) − has three major resonance structures: [O-CuP] − (51.7%), [OvCvP] − (40.2%) and [OuC → P] − (7.1%). 4 Recently, reactivity studies involving these salts has led to the formation of novel heterocycles, [5][6][7][8][9][10][11] main-group small molecules, [12][13][14][15] transition metal complexes, 4,[16][17][18][19] and phosphorus derivatives of organic molecules. 20,21 However, the number of O-bound phosphaethynolate salts are limited as most M x (OCP) y compounds feature M-P instead of M-O bonds.…”

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confidence: 99%

“…20,21 However, the number of O-bound phosphaethynolate salts are limited as most M x (OCP) y compounds feature M-P instead of M-O bonds. 4,[11][12][13][14][15][16]18,19 Thus, the only structurally characterized examples of complexes with M-O-CuP functionalities are of lithium A, 1 calcium B, 22 sodium C, 3 uranium D, 17 and thorium E (Fig. 1).…”

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An isolable magnesium diphosphaethynolate complex

et al. 2018

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The reaction of magnesium chloride with two equivalents of sodium phosphaethynolate, Na[OCP]·(dioxane) (1), yields a magnesium diphosphaethynolate complex, [(THF)Mg(OCP)] (3). The formation of compound 3 goes through a monosubstituted chloromagnesium phosphaethynolate Mg(OCP)Cl (2). The structure of 3 was determined via a single crystal X-ray diffraction study. For comparison, we also report the structure of a monomeric sodium phosphaethynolate complex, [Na(OCP)(dibenzo-18-crown-6)] (4).

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Insertion of sodium phosphaethynolate, Na[OCP], into a zirconium–benzyne complex

Cited by 20 publications

References 35 publications

The Chemistry of the 2‐Phosphaethynolate Anion

The Chemistry of the 2‐Phosphaethynolate Anion

2‐Phospha‐ and 2‐Arsaethynolates – Versatile Building Blocks in Modern Synthetic Chemistry

An isolable magnesium diphosphaethynolate complex

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