New Access to and Reactions of <i>P</i>‐Functional Acylphosphane Complexes

Nesterov, V. I.; Duan, Lili; Schnakenburg, Gregor; Streubel, Rainer

doi:10.1002/ejic.201001122

Cited by 29 publications

(27 citation statements)

References 31 publications

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“…All the products 5a-d, 6, 7a-c, [10] 8, and 9 were fully characterized by multinuclear NMR, IR, MS, and elemental analysis. In addition, the structures of 5a ( Figure 4) and 6 ( Figure 5) were established unequivocally by X-ray crystal analysis.…”

Section: Resultsmentioning

confidence: 99%

“…In addition to this important NMR feature, they show markedly elongated C-E or Si-E bonds (E = Cl, O) in solid-state structures compared with their corresponding non-lithiated derivatives. Reactivity studies on Li/Cl (phosphinidenoid)tungsten complexes [R = CH(SiMe 3 ) 2 , C 5 Me 5 ] revealed nucleophilic reactivity towards organic iodides [9] and acyl chlorides, [10] and phosphinidene-like reactivity towards π-systems such as nitriles, alkynes, and aldehydes. Reactivity studies on Li/Cl (phosphinidenoid)tungsten complexes [R = CH(SiMe 3 ) 2 , C 5 Me 5 ] revealed nucleophilic reactivity towards organic iodides [9] and acyl chlorides, [10] and phosphinidene-like reactivity towards π-systems such as nitriles, alkynes, and aldehydes.…”

Section: Introductionmentioning

confidence: 99%

“…[12] Recently, we gained further insight into these systems. [10] Herein we report the first extensive study on the synthesis and reactions of Li/OR (phosphinidenoid)tungsten complexes. The first single-crystal structure of a P-OPh complex derivative revealed a solvent-separated ion pair by virtue of weakly coordinating cations.…”

Section: Introductionmentioning

confidence: 99%

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P‐OR Functional Phosphanido and/or Li/OR Phosphinidenoid Complexes?

Duan¹,

Schnakenburg²,

Daniels³

et al. 2012

Eur J Inorg Chem

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Keywords: Phosphanes / P ligands / Lithium / Phosphinidenoids / Tungsten / Structure elucidation P-H,P-OR-substituted phosphane complexes 3a-e have been synthesized by two methods: (1) the thermal reaction of 2Hazaphosphirene complex 1 with methanol, n-butanol, or ethylene glycol monomethyl ether (3b,c,e) or (2) the reaction of P-chlorophosphane complex 2 with appropriate sodium phenolate salts (3a,d). All the complexes 3a-e were obtained in good yields and fully characterized by NMR, IR, MS, and elemental analysis. Furthermore, the structures of 3a, 3d and 3e were confirmed unambiguously by X-ray analysis. The de-

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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P‐OR Functional Phosphanido and/or Li/OR Phosphinidenoid Complexes?

Duan¹,

Schnakenburg²,

Daniels³

et al. 2012

Eur J Inorg Chem

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“…The formation and stability of chloroformylphosphane complexes 3a-c was found to be largely dependent on the nature of the substituents at phosphorus, the amounts of phosgene solution employed, and the temperature regime. When phosphinidenoid complex 2a [11] [X = Cl, R = CH(SiMe 3 ) 2 ] was reacted with nearly equimolar amounts of phosgene (20 % solution in toluene) in conditions similar to reported for preparation of analogous organylacylphosphane tungsten(0) complexes [12], no selective formation of the corresponding chloroformylphosphane complex 3a was observed. Instead, rapid formation of dichlorophosphane complex 1a [δ ( 31 P) = 157.6 ppm, 1 J P,W = 330.8 Hz] and some by-products assigned to the chloroformylphosphane complex 3a [δ ( 31 P) = 129.6 ppm, 1 J P,W = 296.3 Hz], chlorophosphane complex 4a [13] [δ ( 31 P) = 53.7 ppm, 1 J P,W = 268.8 Hz, 1 J P,H = 349.4 Hz], and nonidentified species was observed.…”

Section: Resultsmentioning

confidence: 98%

“…For example, 3a possesses a value inbetween those of the dichlorophosphane 1a and the corresponding benzoylphosphane complex [δ ( 31 P) = 113.8 ppm, 1 J P,W = 267.0 Hz] [12] in which the phenyl group is bonded to the carbonyl carbon instead of chlorine. In the 13 C NMR spectra signals of carbonyl carbon atoms of chloroformyl moieties for 3a and 3c were observed as a singlet (at -60 °C) and as a doublet [ 1 J(C,P) = 13.6 Hz; 25 °C] at 176.9 ppm, respectively.…”

Section: Resultsmentioning

confidence: 99%

First synthesis of chloroformylphosphane complexes

Nesterov

Heurich

Streubel

2012

Pure and Applied Chemistry

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An approach to novel P-functional chloroformylphosphane complexes is described using the synthetic potential of lithium/halogeno phosphinidenoid tungsten(0) complexes. Similarly to transition-metal-free chloroformylphosphanes, the obtained complexes tend to eliminate CO via P-C bond cleavage to give the corresponding P-chlorophosphane complex derivatives. Nevertheless, this method allowed the isolation of the first complex derivatives, which will open new synthetic perspectives in organophosphorus chemistry.Scheme 2 Reaction of Li phosphinidenoid complexes 6a,b with phosgene.

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Mechanism of the Phospha‐Wittig–Horner Reaction

et al. 2013

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Phosphaalkenes are prominent ligands in homogenous catalysis due to their p-acceptor capacity [1] and are appealing building blocks in polymer science. [1b, 2] Methods for their preparation are however often limited by small substrate scopes, or residual OTMS substituents that stem from certain synthetic methods.[3] The phospha-Wittig-Horner (pWH) reaction, as first coined by Mathey and co-workers, [4] converts aldehydes and relatively unreactive ketones into C-monoand C,C-disubstituted phosphaalkenes, respectively (Scheme 1, top). Furthermore, the substituent at the phosphorus center can be chosen rather freely, although smaller groups demand additional stabilization by metal coordination.[5] In context of our previous work on the incorporation of low-valent phosphorus into unsaturated carbon scaffolds, [6] we were interested to see whether the scope of the pWH reaction could be extended to ketene substrates from which 1-phosphapropadienes would become accessible. Such phosphaallenes are the shortest members of an intriguing class of P-terminated cumulenes, which have however been synthetically highly challenging with only sporadic reports in the literature. [7] Despite of the synthetic versatility of the pWH reaction, it has been a greatly underexplored method for the preparation of phosphaalkenes. At the same time, the reaction mechanism has hitherto been unknown. Formally, the pWH reaction is the phosphorus analogue to the Horner-WadsworthEmmons reaction (HWE), which allows preparation of alkenes and allenes from carbonyl compounds and ketenes, respectively.[8] The mechanism of the HWE reaction has been studied in great detail over the last decades, with the crucial step being a simultaneous CÀP and CÀO bond cleavage in an intermediately formed oxaphosphetane to afford the desired alkene and the phosphate byproduct (Scheme 1, bottom).[9] In the spirit of the frequently drawn analogy between phosphorus and carbon, [10] it was assumed that the pWH reaction proceeds along a similar pathway. In the present report, we show for the first time that this assumption is wrong and that the pWH reaction proceeds in a more complex, stepwise fashion. The mechanism of the pWH reaction is elucidated with the aid of spectroscopically and crystallographically characterized reaction intermediates.The present study is based on two pWH reagents that are stabilized by {W(CO) 5 } fragments but differ in the P III substituent (1, 2), [5a] and two substrate ketenes, one with phenyl substituents (3), the other with a fused fluorenyl core (4). As for all HWE and pWH reactions, the reactions are initiated by the addition of base. Thus, stoichiometric amounts of organic base (1,8-diazabicyclo[5.4.0]undec-7-ene, DBU) were added to 1 or 2 followed by the addition of either ketene 3 or 4. The products that were obtained after 30 min and aqueous workup were however not the expected phosphaallenes, but previously unknown phosphinophosphates 5 a-d (Scheme 2).Complexes 5 a-d are obtained as pale yellow solids in good to excellent yields. The...

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New Access to and Reactions of P‐Functional Acylphosphane Complexes

Cited by 29 publications

References 31 publications

P‐OR Functional Phosphanido and/or Li/OR Phosphinidenoid Complexes?

P‐OR Functional Phosphanido and/or Li/OR Phosphinidenoid Complexes?

First synthesis of chloroformylphosphane complexes

Mechanism of the Phospha‐Wittig–Horner Reaction

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