Volatile fluorinated alkoxides of the alkali metals

Dear, R. E. A.; Fox, W. B.; Fredericks, Robert J.; Gilbert, Everett E.; Huggins, D. K.

doi:10.1021/ic50093a044

Cited by 52 publications

(15 citation statements)

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“…aquatorialer Position fixierten Gruppen unterschieden werden kdnnen. Im Gegensatz hierzu ist die Ligandenpermutation in 4 bei Raumtemperatur wie in 5 vollstandig ,,eingefroren", wohl durch die Anwesenheit der sehr raumerfullenden t BuNH-und ( zwischen x / a und z/c, V , , und U, .6876 (1) .6158 (3) .6654 (4) .6010 (5) .4387 (6) .3784 (4) .3633 (3) .4264 (4) .6934 (6) .8308 (4) .6953 (5) .6502 (5) .5526 (3) .5200 (5) .4852 (6) .6074 (4) .3853 (4) .4361 (5) .3952 (6) .4301 (4) .2718 (3) .3686 (5) .8216 (3) .8621 (5) .8082 (6) .6630 (4) .8588 (4) .8473(5) 1.0279(5) 1.0635(4) 1.0939(4) 1.0822 (4) .9053 (5) .9073(6) 1.0410 (4) .8246 (5) .9730 (7) .9010 (6) .9713(6) 1.1076 (5) .6707 (13) .5785 (13) .7982 (13) .75a3 (3) .8554 (4) .9547 (13) .2578 (1) .3149 (2) .1530 (3) .2130 (4) .1784 (5) .2450 (4) .1796 (3) .0755 …”

Section: Tab 4 Nmr-daten Der Verbindungen 2aunclassified

“….3727 (4) .1869 (5 ) .0960 (3) .2182 (3) .1566 (4) .3482 (2) .4413 (4) .5442 (4) .5350 (3) .5639 (3) .6315 (3) .4403 (5) .3 5OO ( 3) .4484 (4) .5244 (3) .1819 (2) .1750 (4) .1667 (5) .1594 (4) .2600 (4) .0816(6) -.0133 (4) .0976 (6) .0718 (5) .0904 (13) .2234 (13) .4532 (13) .2361 (13) .oao7 (4) .5688 (1) .4166 (3) .4244 (4) .3123 (5) .2010 (6) .1103 (4) 273614) .1184 (4) .2316 (5) .3314 (4) .1475 (5) .1469 (4) .6009 (3) .7149 (5) .7872 (6) .8665 (4) .6907 (4) .8825 (4) .6398 (7) .5648 (5) .5391 (5) .7399 (6) .6696 (3) .6342 (5) .7012 (6)…”

Section: (3)mentioning

confidence: 99%

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Monocyclische 1,3,2λ ⁵ ‐Oxazaphosphetane

et al. 1985

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Durch Reaktion von Aminodifluorphosphanen RNHPF, (R = H, Me, fBu) mit LiOCH(CF,), entstehen die Amidophosphite l a , c und e, von denen l a und l c wie auch MeNHPF, und t BuNHPFz mit Hexafluoraceton in guten Ausbeuten die bei Raumtemperatur besttindigen 1 ,3,2h5-Oxazaphosphetane 2a -d ergeben. Die Rontgenstrukturanalyse von 2a zeigt eine verzerrte trigonale Bipyramide. Monocyclic 1,3,215-0xazaphosphetanes The reactions of aminodifluorophosphanes RNHPF, (R = H, Me, tBu) with LiOCH(CF,), yield the amidophosphites l a , c, and e. Compounds l a and c as well as MeNHPF2 and tBuNHPF2 add hexafluoroacetone to give in good yields the 1,3,2hs-oxazaphosphetanes 2a-d, which are stable at room temperature. The X-ray structure analysis of 2a exhibits a distorted trigonal bipyramid. 4,4,5,5-Tetrakis(trifluormethyl)-l,3,2-dioxaphospholan-2-amin, ein monocyclisches Amidophosphit, addiert Hexafluoraceton unter Bildung eines spirocyclischen 1 ,3,2h5-Oxazaphosphetans'), das bei Raumtemperatur keine Substituenten-Permutationen mehr aufweist . Bei gleichen Reaktionsbedingungen liefert Aminodifluorphosphan hingegen nur die Zerfallsprodukte einer moglichen Oxazaphosphetan-Zwischenstufe. Die Reaktionen von einigen ausgewahlten Aminophosphanen und Amidophosphiten RNHPX, mit Hexafluoraceton sollten klaren, ob durch GroBenanderung der Reste an Stickstoff (R = H, Me, tBu) bzw. an Phosphor (R = F, OCH(CF,),) thermisch bestandige 1 ,3,2hs-Oxazaphosphetane zu erhalten sind, deren dynamisches Verhalten von Interesse ist. Experimentelle Ergebnisse Die Amidophosphite l a , c und e, niedrig siedende, farblose Fliissigkeiten, waren in guten Ausbeuten durch F/OCH(CF,),-Austausch aus den Aminodifluorphosphanen RNHPF, (R = H, Me", tBu3)) und Lithium-2,2,2-trifluor-l-(trifluormethyl)ethano-lat4) zuganglich [GI. (l)]. AuOer l e ergaben die Phosphor(II1)-Verbindungen l ad mit Hexafluoraceton bei Raumtemperatur bestandige, nicht hydrolyseempfindliche Oxazaphosphetane 2a -d [GI. (2)] (zwei Reaktionswege wurden schon in Lit.') vorgeschlagen). 0 VCH Verlagsgesellschaft mbH, D-

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Section: Tab 4 Nmr-daten Der Verbindungen 2aunclassified

Section: (3)mentioning

confidence: 99%

Monocyclische 1,3,2λ ⁵ ‐Oxazaphosphetane

et al. 1985

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“…Bis-ieri-butyl chlorophosphine does not react with 1 even when the reaction mixture is refluxed for six hours. On the other hand ierf-butyl methyl chlorophosphine [7] reacts readily with 1 to form £erf-butyl-methyl-(hexafluoroisopropyl)phosphite (12) in good yield. These results suggest the operation of a combination of electronic and steric effects which hinder formation of tertbutyl-bis-(hexafluoroisopropyl)phosphite.…”

Section: P[och(cf3)mentioning

confidence: 99%

“…The tube was allowed to warm to room temperature over lh and then left for a further 2 h. The colourless liquid, 12 We thank Deutsche Forschungsgemeinschaft for financial support and for providing an NMR instrument. One of us (D. D.) acknowledges the award of an Alexander von Humboldt Fellowship.…”

Section: Tert-butyl-methyl-(lll333-hexafluoroisopropyl )-Phosphimentioning

confidence: 99%

Synthesis of Chiral and Non-chiral Phosphites Containing the Hexafluoroisopropoxy Group

Dakternieks

Röschenthaler

Schmutzler

1978

Zeitschrift Für Naturforschung B

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“…Although a definite decision cannot be made, we suggest that, in this case, reaction has stopped at the second stage of the above scheme, with one C ( C F , ) , Ogroup coordinated to the sodium ion rather than the copper ion. The remarkable stability of fluorinated sodiuni alkoxides of this type has been demonstrated by the properties of the sodium derivative of perfluoro-t-butanoi, (CF,),CONa, which may be distilled without decomposition (14).…”

Section: Reactions Of Tlze Coordinated Ligandmentioning

confidence: 99%

Fluorinated Alkoxides Part VII. Complexes of 2-Acetamidohexafluoro-2-propanol with First-row Transition and Lanthanide Elements

Macdonald¹,

Willis²

1973

Can. J. Chem.

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2-Acetamidohexafluoro-2-propanol (HAcfp), CH3CONHC(CF3)2OH, may act as a bidentate, uninegative, ligand to give complexes of the type M(Acfp)2 (M = Co2+, Ni2+, Cu2+, Zn2+); M(Acfp)3 (M = Fe3+); M(Acfp)4 (M = Ce4+); or [M(Acfp)4]− (M = lanthanide(III)). Coordination is through the two oxygen atoms, except in the case of copper, where nitrogen also enters into coordination. In the complex Cu(Acfp)2, the amido proton may be removed with NaH to give Na2[Cu(Acfp)2], which undergoes addition reactions with carbonyl groups.Formamide similarly undergoes reaction with hexafluoroacetone to give HCONHC(CF3)2OH, which chelates to copper in the same manner as HAcfp, while succinic acid diamide reacts with hexafluoroacetone to give the compound [—CH2CONHC(CF3)2OH]2, which acts as a tetradentate, dinegative, ligand.Possible structures of the above complexes are discussed.

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Volatile fluorinated alkoxides of the alkali metals

Cited by 52 publications

References 0 publications

Monocyclische 1,3,2λ ⁵ ‐Oxazaphosphetane

Monocyclische 1,3,2λ ⁵ ‐Oxazaphosphetane

Synthesis of Chiral and Non-chiral Phosphites Containing the Hexafluoroisopropoxy Group

Fluorinated Alkoxides Part VII. Complexes of 2-Acetamidohexafluoro-2-propanol with First-row Transition and Lanthanide Elements

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Volatile fluorinated alkoxides of the alkali metals

Cited by 52 publications

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Monocyclische 1,3,2λ 5 ‐Oxazaphosphetane

Monocyclische 1,3,2λ 5 ‐Oxazaphosphetane

Synthesis of Chiral and Non-chiral Phosphites Containing the Hexafluoroisopropoxy Group

Fluorinated Alkoxides Part VII. Complexes of 2-Acetamidohexafluoro-2-propanol with First-row Transition and Lanthanide Elements

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Monocyclische 1,3,2λ ⁵ ‐Oxazaphosphetane

Monocyclische 1,3,2λ ⁵ ‐Oxazaphosphetane