An unconventional route to [(Me3Si)2HCPCl2W(CO)5] and its conversion to the structurally characterized P-chalcogenides (Me3Si)2HCP(X)Cl2 [X = S, Se]

Khan, Arif; Wismach, Cathleen; Jones, Peter G.; Streubel, Rainer

doi:10.1039/b301775c

Cited by 40 publications

(34 citation statements)

References 17 publications

(6 reference statements)

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“…With the exception of the acid 6 a, the IR spectra show typical absorptions for the BÀH and PÀH valence stretching frequencies at about 2400 and 2300 cm ). [19] In the solid state, 6 a shows a typical P=O stretching frequency at 1217 cm À1 and furthermore a broad band at 2954 cm À1 for the POH frequency, which indicates hydrogen bonds. , which contains a coordinative PÀB bond.…”

Section: à3mentioning

confidence: 99%

Lewis Base Stabilized Phosphanylborane

Schwan

Timoskin

Zabel

et al. 2006

Chemistry A European J

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The abstraction of the Lewis acid from [W(CO)(5)(PH(2)BH(2)NMe(3))] (1) by an excess of P(OMe(3))(3) leads to the quantitative formation of the first Lewis base stabilized monomeric parent compound of phosphanylborane [H(2)PBH(2)NMe(3)] 2. Density functional theory (DFT) calculations have shown a low energetic difference between the crystallographically determined antiperiplanar arrangement of the lone pair and the trimethylamine group relative to the P-B core and the synperiplanar conformation. Subsequent reactions with the main-group Lewis acid BH(3) as well as with an [Fe(CO)(4)] unit as a transition-metal Lewis acid led to the formation of [(BH(3))PH(2)BH(2)NMe(3)] (3), containing a central H(3)B-PH(2)-BH(2) unit, and [Fe(CO)(4)(PH(2)BH(2)NMe(3))] (4), respectively. In oxidation processes with O(2), Me(3)NO, elemental sulfur, and selenium, the boranylphosphine chalcogenides [H(2)P(Q)BH(2)NMe(3)] (Q = S 5 b; Se 5 c) as well as the novel boranyl phosphonic acid [(HO)(2)P(O)BH(2)NMe(3)] (6 a) are formed. All products have been characterized by spectroscopic as well as by single-crystal X-ray structure analysis.

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Section: à3mentioning

confidence: 99%

Lewis Base Stabilized Phosphanylborane

Schwan

Timoskin

Zabel

et al. 2006

Chemistry A European J

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“…When phenylacetylene was used as reagent, another product 10 was observed which could not be isolated (products 9/10 in a ratio of 5:1) and had a signal in the 31 P NMR spectrum at d = À78.3 ppm and coupling constants of 1 J(W,P) = 235.2 Hz and 1 J(P,H) = 354.8 Hz. Chlorine/lithium exchange of dichloro(organo)phosphane complex 11 [19] using tert-butyllithium at low temperature in the presence of [12]crown-4 along with benzaldehyde or butyraldehyde gave easier access to the phosphinidenoid complex 2, yielding selectively oxaphosphirane complexes 8 [18] and 12, respectively (Scheme 5). All complexes were purified by column chromatography and fully characterized by NMR spectroscopy, mass spectrometry, and elemental analysis.…”

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confidence: 98%

Strong Evidence for a Transient Phosphinidenoid Complex

et al. 2007

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“…Einen einfacheren Zugang zum Phosphinidenoid-Komplex 2 eröffnete der Chlor/Lithium-Austausch am Dichlor-(organo)phosphan-Komplex 11 [19] mit tert-Butyllithium bei tiefer Temperatur; mit [12]Krone-4 und Benzaldehyd oder Butyraldehyd wurden so selektiv die Oxaphosphiran-Komplexe 8 [18] bzw. 12 erhalten (Schema 5).…”

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