(Dialkylamino)phosphines and their metal carbonyl complexes

King, R. B.; Sadanani, N. D.

doi:10.1021/ic00214a011

Cited by 34 publications

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“…[41] nButyllithium (35.4 mL of a 1.6 m solution in hexanes, 56.7 mmol) was slowly added to a solution of p-CF 3 C 6 H 4 Br (12.8 g, 56.7 mmol) in diethyl ether (400 mL) at 5 8C. The mixture was stirred for 3 h, and Et 2 NPCl 2 (4.93 g, 28.3 mmol) was slowly introduced into the flask at 5 8C.…”

Section: Electron-beam Lithography (Ebl)mentioning

confidence: 99%

Rhodium‐Catalyzed Dehydrocoupling of Fluorinated Phosphine–Borane Adducts: Synthesis, Characterization, and Properties of Cyclic and Polymeric Phosphinoboranes with Electron‐Withdrawing Substituents at Phosphorus

Clark

Rodezno

Clendenning

et al. 2005

Chemistry A European J

118

112

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The dehydrocoupling of the fluorinated secondary phosphine-borane adduct R2PH.BH3 (R = p-CF3C6H4) at 60 degrees C is catalyzed by the rhodium complex [{Rh(mu-Cl)(1,5-cod)}2] to give the four-membered chain R2PH-BH2-R2P-BH3. A mixture of the cyclic trimer [R2P-BH2]3 and tetramer [R2P-BH2]4 was obtained from the same reaction at a more elevated temperature of 100 degrees C. The analogous rhodium-catalyzed dehydrocoupling of the primary phosphine-borane adduct RPH2.BH3 at 60 degrees C gave the high molecular weight polyphosphinoborane polymer [RPH-BH2]n (Mw = 56,170, PDI = 1.67). The molecular weight was investigated by gel permeation chromatography and the compound characterized by multinuclear NMR spectroscopy. Interestingly, the electron-withdrawing fluorinated aryl substituents have an important influence on the reactivity as the dehydrocoupling process occurred efficiently at the mildest temperatures observed for phosphine-borane adducts to date. Thin films of polymeric [RPH-BH2]n (R = p-CF3C6H4) have also been shown to function as effective negative-tone resists towards electron beam (e-beam) lithography (EBL). The resultant patterned bars were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and time-of-flight secondary ion mass spectrometry (TOF-SIMS).

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Section: Electron-beam Lithography (Ebl)mentioning

confidence: 99%

Rhodium‐Catalyzed Dehydrocoupling of Fluorinated Phosphine–Borane Adducts: Synthesis, Characterization, and Properties of Cyclic and Polymeric Phosphinoboranes with Electron‐Withdrawing Substituents at Phosphorus

Clark

Rodezno

Clendenning

et al. 2005

Chemistry A European J

118

112

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“…This type of cation has been used previously in cycloadditions [25]. The ion 40 was preformed as shown in Equation 12 by halide abstraction from dichloro(di-isopropylamino)phosphine with aluminum chloride, as reported earlier [26] The cycloaddition is quite rapid at -78° C ; the usual McCormack reactions, on the other hand, require days or weeks for completion. Two phospholes (42, 28.40 and 43, 35.19) have been prepared by this method, in yields of 68% and 84%, respectively.…”

Section: Thfmentioning

confidence: 99%

The Continuing Development of the Chemistry of Phospholes

Quin¹

2006

COC

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The last five years have seen many advances in the chemistry of phospholes. Motivating much of the work has been the potential for discovering valuable applications of phospholes, especially as ligands in metal coordination compounds designed for use as homogeneous catalysts, and in the field of electro-optical substances. This review covers the research in the synthesis, properties and applications of phospholes that has been published since the last comprehensive review by the author in 1999. While prepared for the specialist, the review is designed to introduce some of the aspects of phosphole chemistry to the general reader.

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“…The compound [Co 2 (CO) 6 {µ 2 -P(TMP)}] was prepared and used in situ from the reaction of K[Co(CO) 4 ] and PCl 2 (TMP) (11). PCl 2 (N-i-Pr 2 ) and PCl 2 (TMP) were prepared according to published procedures (21) as was KC 8 (22) and [Co 2 (CO) 8 ] was purchased from Fluka. The NMR spectra were recorded on a Bruker Avance 400 spectrometer at 400 MHz ( 1 H) or 161.975 ( 31 P{ 1 H}).…”

Section: Methodsmentioning

confidence: 99%

Synthesis and transformations of 60-, 62-, and 64-electron Co₄(CO)_x(PNR₂)₂(x= 8, 9, 10) clusters

Sánchez‐Nieves¹,

Sterenberg²,

Udachin³

et al. 2004

Can. J. Chem.

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A unique family of bis-(amino)phosphinidene Co 4 clusters with electron counts in the 60-64 e regime is described. The 62-electron (5 Co-Co) butterfly compound [Co 4 (CO) 8 (µ-CO){µ 3 -P(TMP)} 2 ] (TMP = 2,2,6,6-tetramethylpiperidyl) (1a) is obtained via condensation of the bridged (amino)phosphinidene complex [Co 2 (CO) 6 {µ-P(TMP)}]. Further heating and removal of CO gives the 60-electron (6 Co-Co) tetrahedral compound [Co 4 (CO) 6 (µ-CO) 2 {µ 3 -P(TMP)} 2 ] (3a). The reaction of K[Co(CO) 4 ] with PCl 2 (N-i-Pr 2 ) gives the 64-electron (4 Co-Co) square-planar derivative [Co 4 (CO) 8 (µ-CO) 2 (µ 4 -PN-i-Pr 2 ) 2 ] (2), which loses one carbonyl ligand to form the 62-electron (5 Co-Co) butterfly compound [Co 4 (CO) 8 (µ-CO)(µ 3 -PN-i-Pr 2 ) 2 ] (1b). Complex 1b releases another carbonyl to form the 60-electron (6 Co-Co) tetrahedral compound [Co 4 (CO) 6 (µ-CO) 2 (µ 3 -PN-i-Pr 2 ) 2 ] (3b). X-ray structural analyses of compounds 1a, 1b, 2, and 3a have been carried out. The reversibility of the CO elimination reactions and the structural rearrangements accompanying changes in electron count in this series are discussed. Résumé :On décrit une famille unique d'agrégats de la famille du bis-(amino)phosphinidène Co 4 comportant de 60 à 64 électrons. Le composé en forme de papille comportant 62 électrons (5 Co-Co), le [Co 4 (CO) 8 (µ-CO){µ 3 -P(TMP)} 2 ] (TMP = 2,2,6,6-tétraméthylpipéridyl) (1a) est obtenu par condensation du complexe (amino)phosphinidène ponté [Co 2 (CO) 6 {µ-P(TMP)}]. Un chauffage additionnel avec élimination du CO conduit au composé tétraédrique à 60 élec-trons (6 Co-Co) [Co 4 (CO) 6 (µ-CO) 2 {µ 3 -P(TMP)} 2 ] (3a). La réaction du K[Co(CO) 4 ] avec le PCl 2 (N-i-Pr 2 ) 2 conduit au dérivé plan carré à 64 électrons (4 Co-Co) [Co 4 (CO) 8 (µ-CO) 2 (µ 4 -PN-i-Pr 2 ) 2 ] (2) qui perd un ligand carbonyle pour former le composé en forme de papillon comportant 62 électrons (5 Co-Co), le [Co 4 (CO) 8 (µ-CO)(µ 3 -PN-i-Pr 2 ) 2 ] (1b). Le composé 1b perd un autre ligand carbonyle pour former le composé tétraédrique à 60 électrons (6 Co-Co) [Co 4 (CO) 6 (µ-CO) 2 (µ 3 -PN-i-Pr 2 ) 2 ] (3b). On a déterminé les structures des composés 1a, 1b, 2 et 3a par diffraction des rayons X. On discute de la réversibilité des réactions d'élimination du CO et des réarrangements de structure qui accompagnent les changements dans les nombres d'électrons dans ces séries.

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(Dialkylamino)phosphines and their metal carbonyl complexes

Cited by 34 publications

References 0 publications

Rhodium‐Catalyzed Dehydrocoupling of Fluorinated Phosphine–Borane Adducts: Synthesis, Characterization, and Properties of Cyclic and Polymeric Phosphinoboranes with Electron‐Withdrawing Substituents at Phosphorus

Rhodium‐Catalyzed Dehydrocoupling of Fluorinated Phosphine–Borane Adducts: Synthesis, Characterization, and Properties of Cyclic and Polymeric Phosphinoboranes with Electron‐Withdrawing Substituents at Phosphorus

The Continuing Development of the Chemistry of Phospholes

Synthesis and transformations of 60-, 62-, and 64-electron Co₄(CO)_x(PNR₂)₂(x= 8, 9, 10) clusters

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(Dialkylamino)phosphines and their metal carbonyl complexes

Cited by 34 publications

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Rhodium‐Catalyzed Dehydrocoupling of Fluorinated Phosphine–Borane Adducts: Synthesis, Characterization, and Properties of Cyclic and Polymeric Phosphinoboranes with Electron‐Withdrawing Substituents at Phosphorus

Rhodium‐Catalyzed Dehydrocoupling of Fluorinated Phosphine–Borane Adducts: Synthesis, Characterization, and Properties of Cyclic and Polymeric Phosphinoboranes with Electron‐Withdrawing Substituents at Phosphorus

The Continuing Development of the Chemistry of Phospholes

Synthesis and transformations of 60-, 62-, and 64-electron Co4(CO)x(PNR2)2(x= 8, 9, 10) clusters

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Synthesis and transformations of 60-, 62-, and 64-electron Co₄(CO)_x(PNR₂)₂(x= 8, 9, 10) clusters