Synthesis of the First 2H-1,2-Azaphosphole Complexes with P,C and P,N Ylide Functional Groups

Streubel, Rainer; Hoffmann, Nils; Schiebel, Hans‐Martin; Ruthe, Frank; Jones, Peter G.

doi:10.1002/1099-0682(200203)2002:4<957::aid-ejic957>3.0.co;2-2

Cited by 10 publications

(11 citation statements)

References 23 publications

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“…ref ) failed. This thermal stability of 11a − d is in marked contrast to that of the corresponding bulky P -bis(trimethylsilyl)methyl-substituted 2 H -1,2-azaphosphole complex 11e , which yields the noncoordinated 2 H -1,2-azaphosphole under the same reaction conditions . Initial studies of cleavage reactions of the exocyclic P−C bonds of 2 H -1,2-azaphosphole complexes 11a and 11b showed instantaneous reactions of 11a , b with potassium tert -butanolate (KO t Bu) at ambient temperature (cf.…”

Section: Resultsmentioning

confidence: 91%

“…We knew from our recent studies that three-component reactions using 2 H -azaphosphirene complexes, alkynes, and carbonitriles with strong π-donating substituents such as the triphenylphosphane-imino substituent yield transient nitrilium phosphane-ylide complexes that react more selectively than C - dialkylamino-substituted derivatives. Therefore, we decided to carry out a comparative study using the 7-phosphanorbornadiene complexes 3a , 3b , and 3c , d , the carbonitrile derivative 4b , and DMAD ( 5 ).…”

Section: Resultsmentioning

confidence: 99%

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Multifunctional 2H-1,2-Azaphosphole Complexes: A Good Starting Point for the Synthesis of Functional 1,2-Azaphospholide Complexes?

et al. 2003

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The thermolysis of P-functionalized 7-phosphanorbornadiene tungsten complexes 3a−d in o-xylene at 120 °C in the presence of various carbonitriles and dimethyl acetylenedicarboxylate (DMAD) has been investigated. The reaction of complex 3a, 1-piperidino carbonitrile, and DMAD yielded a product mixture, whereby 2H-1,2-azaphosphole complex 6 was formed in ca. 40−45% yield together with diazaphosphole complexes 7 (ca. 10−15%) and 8 (ca. 10−15%) and other nonidentified products (ca. 30%). Unfortunately, none of these products could be separated by column chromatography. In marked contrast, reactions of 7-phosphanorbornadiene tungsten complexes 3a−d with triphenylphosphane-imino carbonitrile and DMAD led to P-functionalized 2H-1,2-azaphosphole complexes 11a−d in good to excellent yields. Preliminary investigations of decomplexation reactions revealed a remarkable thermal stability of 11a−d: no reaction occurred with bis(diphenylphosphino)ethane (DPPE) at 140 °C. Preliminary studies of exocyclic P−C bond cleavage reactions of 2H-1,2-azaphosphole complexes 11a,b using potassium tert-butanolate (KOtBu) showed instantaneous reactions and color change from yellow to dark red; an intermediate was detected by 31P NMR spectroscopy. Treatment with an excess of methyl iodide led to one major product, which, most probably, is the N-methyl-substituted 1H-1,2-azaphosphole complex 13; unfortunately, chromatography failed and it could only be observed by 31P NMR spectroscopy. A comparative study on P−C bond cleavage/methylation reactions using monofunctional 2H-1,3,2-diazaphosphole complex 14 and the system KOtBu/methyl iodide showed the selective formation of the P-methyl-substituted 2H-1,3,2-diazaphosphole complex 16; complexes 14 and 16 were prepared using the Cu(I)Cl route. Complexes 11a−d, 14, and 16 were characterized by elemental analyses, NMR, UV/vis, IR, and mass spectroscopy and, in addition, by single-crystal X-ray diffraction in the case of 11a−d. Additionally, we investigated selected isomers of lithium and potassium 1,2-azaphospholides by ab initio calculations using HF and MP2/6-311++G(2d,p) level of theory; stability, structure, and aromaticity aspects are discussed.

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Section: Resultsmentioning

confidence: 91%

Section: Resultsmentioning

confidence: 99%

Multifunctional 2H-1,2-Azaphosphole Complexes: A Good Starting Point for the Synthesis of Functional 1,2-Azaphospholide Complexes?

et al. 2003

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“…Furthermore, the reaction of complex 56 with 2-(triphenyl- 5 -phosphanyl)acetonitrile led to the formation of 1,2-azaphosphole 59 (Scheme 18). 33,[48][49][50]…”

Section: Scheme 17mentioning

confidence: 99%

“…Also, reaction of complex 56 with ethyl propiolate and different nitriles in pentane gave 1,2-azaphospholes 65 in high yield (Scheme 20). 49,50,52,54…”

Section: Scheme 19mentioning

confidence: 99%

The synthesis of 1,2-azaphospholes, 1,2-azaphosphorines and 1,2-azaphosphepines

Hassanin¹,

Ali²,

Assiri³

et al. 2020

Arkivoc

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“…The crystal structures for 8 (R = 1,5-dimethylpyrrol-2-yl) and 9 (R = 2-thienyl, 1,5-dimethylpyrrol-2-yl) were determined. 134 The dibismuthene complex, [{µ-η 2 -(cis-Me 3 SiCH 2 Bi) 2 }{W(CO) 5 } 2 ] 10, was formed from reaction of [W(CO) 5 (THF)] with an equilibrium mixture of five-and threemembered cycloalkylbismuthenes. 135…”

Section: Nitrogen-donor Ligandsmentioning

confidence: 99%

12 Chromium, molybdenum and tungsten

Malito

2003

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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Synthesis of the First 2H-1,2-Azaphosphole Complexes with P,C and P,N Ylide Functional Groups

Abstract: The first C 5 -functionalized 2H-1,2-azaphosphole complexes have been obtained by the reactions of P,C and P,N ylide substituted carbonitriles and terminal phosphanediyl complexes involving transiently formed nitrilium phosphanylide complexes.

Cited by 10 publications

References 23 publications

Multifunctional 2H-1,2-Azaphosphole Complexes: A Good Starting Point for the Synthesis of Functional 1,2-Azaphospholide Complexes?

Multifunctional 2H-1,2-Azaphosphole Complexes: A Good Starting Point for the Synthesis of Functional 1,2-Azaphospholide Complexes?

The synthesis of 1,2-azaphospholes, 1,2-azaphosphorines and 1,2-azaphosphepines

12 Chromium, molybdenum and tungsten

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