Reactivity of Carbonyl-Functionalized Phosphaalkenes RC(O)P=C(NMe2)2 (R =tBu, Ph) towards Electrophiles

Weber, Lothar; Uthmann, Stefan; Stammler, Hans‐Georg; Neumann, Beate; Schoeller, Wolfgang W.; Boese, Roland; Bläser, Dieter

doi:10.1002/(sici)1099-0682(199912)1999:12<2369::aid-ejic2369>3.0.co;2-s

Cited by 20 publications

(13 citation statements)

References 41 publications

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“…Setzt man demgegenüber das invers-polarisierte Phosphaalken II mit 1a um, so wird der entsprechende Metallaheterocyclus IV neben dem Hauptprodukt V nur in untergeordnetem Maße gebildet [7] (Schema 1).…”

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Zur Reaktivität des Ferriophosphaalkens (Z)-[Cp*(CO)2FeP=C(tBu)NMe2] gegenüber Propiolsäureestern HC≡C-CO2R (R=Me, Et) und Acetylendicarbonsäureestern RO2C-C≡C-CO2R (R=Me, Et, tBu)

Weber¹,

Kleinebekel²,

Lönnecke³

2002

Z. anorg. allg. Chem.

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Inhaltsübersicht. Bei der Umsetzung äquimolarer Mengen an [(Z)-Cp*(CO) 2 FePϭC(tBu)NMe 2 ] (3) mit den Propiolsäureestern HCϵC-CO 2 R 2(a:RϭMe, b:Et) sowie den Acetylendicarbonsäure-estern RO 2 C-CϵC-CO 2 R 1(a:RϭMe, b:Et, c:tBu) bilden sich fünf-gliedrige Metallaheterocyclen On the Reactivity of the Ferriophosphaalkene (Z)-[Cp*(CO) 2 Fe-P‫؍‬C(tBu)NMe 2 ] towards Propiolates HCϵC-CO 2 R (R‫؍‬Me, Et) and Acetylene Dicarboxylates RO 2 C-CϵC-CO 2 R (R‫؍‬Me, Et, tBu).Abstract. The reaction of equimolar amounts of (Z)-[Cp*(CO) 2-FePϭC(tBu)NMe 2 ] 3 and methyl-and ethyl-propiolate (2a, b) or of 3 and dialkyl acetylene dicarboxylates 1a (RϭMe), 1b (Et), 1c(tBu) afforded the five-membered metallaheterocycles [Cp*(CO)F Te-C(ϭO)-C(CO 2 R)ϭCHP UϭC(tBu)NMe 2 ] (4a,b) and [Cp*(CO)F Te-C(ϭO)-C(CO 2 R)ϭC(CO 2 R)-P UϭC(tBu)NMe 2 ] (5a؊c). The mole-1 Einleitung

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“…Wie bei den Ausgangsmaterialien I und II schon beobachtet, unterscheiden sich auch die 31 P-NMR-Signale der Cycloaddukte III (δϭ357.7) [5] und IV (δϭ72.4) [7] signifikant und deuten auf eine trigonal-planare Geometrie am PAtom in III und auf trigonal-pyramidalen Phosphor in IV hin. Letzteres wurde durch die Röntgenstrukturanalyse auch belegt.…”

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Zur Reaktivität des Ferriophosphaalkens (Z)-[Cp*(CO)2FeP=C(tBu)NMe2] gegenüber Propiolsäureestern HC≡C-CO2R (R=Me, Et) und Acetylendicarbonsäureestern RO2C-C≡C-CO2R (R=Me, Et, tBu)

Weber¹,

Kleinebekel²,

Lönnecke³

2002

Z. anorg. allg. Chem.

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“…The solid state X‐ray structure of 5 , shown in Figure , shows that the neutral N,O ‐ ketimine ligand is coordinated to gallium through oxygen in a monodentate κ 1 O‐ coordination mode similar to those of [OCMeCHCMeN(H)( t Bu)]GaMe 3 and [OCMeCMe‐CMeN(H)(Dipp)]ECl 3 (E=Ga and Sb),.The Ga−O bond distance of 1.9812(12) Å is significantly smaller as compared to [OCMeCHCMeN(H)( t Bu)]GaMe 3 (2.0521(6)Å) and [ t BuC(OGa‐Me 3 )=P(GaMe 3 )C(NMe 2 ) 2 (Ga−O=2.109(2) Å) . Complex 5 features a distorted tetrahedral geometry around Ga center with a wide range of angles (89.88(4)‐108.16(8)°).…”

Section: Resultsmentioning

confidence: 98%

Synthesis, Structure and Chemistry of Mono‐ and Digallane Complexes Supported by N,O‐Ketimine Ligand

et al. 2017

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A series of N,O‐ketimine supported gallium and digallane complexes have been synthesized and structurally characterized. The mono(ketiminate) gallium dichloride [OCMeCHCMeN(Dipp)]GaCl2, 2 (Dipp=2,6‐iPr2C6H3) and bis(ketiminate) gallium chloride [OCMeCHCMeN(Dipp)]2GaCl, 3 were isolated from the reaction of GaCl3 with 1 and 2 equivalents of lithiated ketimine, [OCMeCHCMeN(Dipp)]Li, 1 respectively. Treatment of 1 with ‘‘GaI’’ yielded diiodobis(ketiminate) digallane complex [OCMeCHCMeN‐(Dipp)]2Ga2I2, 4. To the best of our knowledge, compound 4 is the first report on N,O‐ketiminate ligand supported stable heteroleptic digallane(II) complex. The frontier molecular orbital analysis and a high Wiberg Bond Index (WBI) values support the strong interaction between the gallium centers in 4. In an attempt to synthesize alkyl substituted Ga complexes, we carried out the reaction of ketimine ligand with GatBu2Cl (1:1 ratio) that generated the adduct [OCMeCHCMeN(H)(Dipp)]GatBu2Cl, 5. In a similar fashion, dialkyl gallium complex [OCMeCHCMeN(Dipp)]GatBu2, 6 was obtained from the reaction of 1 with GatBu2Cl. All the compounds have been charecterized by 1H, 13C NMR and mass spectroscopy. The molecular structures of complexes 2–5 have also been determined by single crystal X‐ray diffraction analysis.

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“…7 The P-acyl derivatives RC(CO)PdC(NMe) 2 are also inversely polarized phosphaalkenes. 8 (1) Laali, K. K.; Geissler, B.; Regitz, M.; Houser, J. J. J. Org. Chem.…”

Section: Introductionmentioning

confidence: 99%

“…The coordination chemistry of metallophosphaalkenes and their reactivity toward electrophiles and carbenes has received considerable attention during the past decade. , Consistent with canonical forms 1 and 1 ‘, protonation, alkylation, and silylation are directed to phosphorus, yielding metallophosphanyl-functionalized carbocations . The P-acyl derivatives RC(CO)PC(NMe) 2 are also inversely polarized phosphaalkenes 3 …”

Section: Introductionmentioning

confidence: 99%

Gas-Phase Synthesis and Characterization of an Azaphosphirenium Ion: The First N,P-Analogue of the Aromatic Cyclopropenyl Cation

2001

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The 3-(dimethylamino)-1,1-dimethyl-1H-azaphosphiren-1-ium ion (3), the first member of the hitherto unknown class of azaphosphirenium ions and the first N,P-analogue of the aromatic cyclopropenyl cation, is generated in the gas phase via 70 eV electron ionization and demetalation of a ferriphosphaalkene (1) and rapid cyclization of the incipient phosphavinyl cation (2). Spontaneous cyclization of 2 to 3 is predicted by Becke3LYP/6-311++G(d,p) calculations, and the structure and reactivity of 3 is probed via collision-induced dissociation and ion-molecule reactions performed via pentaquadrupole mass spectrometry. Gaseous 3 fails to coordinate efficiently with nitrogen and oxygen nucleophiles, but it forms stable adduct ions with phosphorus and sulfur nucleophiles. The adducts of 3 with P and S nucleophiles are likely favored by the incorporation of relatively strong and rare PdS and PdP bonds and through extensive charge delocalization involving dimethylamino substituents. With isoprene, an adduct ion is also readily formed presumably via [4 + 2 + ] cycloaddition (followed by spontaneous ring opening), a reaction which is well documented for phosphenium ions both in solution and in the gas phase.

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Reactivity of Carbonyl-Functionalized Phosphaalkenes RC(O)P=C(NMe2)2 (R =tBu, Ph) towards Electrophiles

Cited by 20 publications

References 41 publications

Zur Reaktivität des Ferriophosphaalkens (Z)-[Cp*(CO)2FeP=C(tBu)NMe2] gegenüber Propiolsäureestern HC≡C-CO2R (R=Me, Et) und Acetylendicarbonsäureestern RO2C-C≡C-CO2R (R=Me, Et, tBu)

Zur Reaktivität des Ferriophosphaalkens (Z)-[Cp*(CO)2FeP=C(tBu)NMe2] gegenüber Propiolsäureestern HC≡C-CO2R (R=Me, Et) und Acetylendicarbonsäureestern RO2C-C≡C-CO2R (R=Me, Et, tBu)

Synthesis, Structure and Chemistry of Mono‐ and Digallane Complexes Supported by N,O‐Ketimine Ligand

Gas-Phase Synthesis and Characterization of an Azaphosphirenium Ion: The First N,P-Analogue of the Aromatic Cyclopropenyl Cation

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