Phosphines, alkylation

Typical reactions are amine or phosphine alkylation or addition to a carbonyl group (Scheme 3.3). In these examples, because of the development of dipoles in the TS, we are concerned with a polarity increase during the course of the reaction starting from the GS towards the TS. Favorable microwave effects are, consequently, expected. 

Phosphine, alkyl phosphines, and monophosphinate esters also produce intense chemiluminescence with F2 [68], Again, these compounds have low ionization potentials and are expected to form charge transfer complexes with F2 [7], The emission spectra obtained in the reaction of trimethyl phosphine (TMP) with excess F2 have contributions from HCF, I IF1, and an unidentified broad-band emission as shown in Figure 9. The relative contributions of HCF and the un-... 

Scheme 28 Cathodic cyclization of unsaturated acids in the presence of triphenyl phosphine alkyl, H, aryl, R H, aryl, yields 11 -49%.

Flausoul PJC, Parvulescu AN, Lutz M, Spek AL, Bruijnincx PCA, Klein GRJM, Weckhuysen BM (2011) Mechanistic study of the Pd/TOMPP-catalyzed telomerization of 1,3-butadiene with biomass-based alcohols on the reversibility of phosphine alkylation. ChemCatChem 3 845-852... 

Phosphine ligand compounds of Mnlv are confined to the phosphine alkyls of Section 41.5.1, and [MnCl2(diphos)2]Cl2 of Table 17 (Section 41.3.4). There are no authenicated arsine compounds. 

Treatment of Ir(CO)Cl(PPh3)2 (29) with alkyl or aryl grignard reagents produces the corresponding alkyl or aryl iridium complexes R-Ir(CO)(PPh3)2 (63). These compounds are substantially more stable than the frilly phosphinated alkyl iridium compounds. The stability of these compounds also increases in the order aryl > alkyl with the fluoro substituted aryl complexes being the most stable. 

Natural Products.—A number of one-step olefin syntheses have appeared in which phosphine, alkyl halide, and carbonyl compound are allowed to react together in the presence of a suitable epoxide as the source of base. Among them are the synthesis of ( )-mitorubrin and of the polyene (97) (Scheme 5). ... 

Phosphorus ligand compounds of Mn ", except for alkyl and hydride species (Section 41.4.6), are confined to a report of [MnCl2(diphos)2]Cl (see Section 41.3.4 and Table 17) and now the unexpected, dark-green, phosphine-iodo compound [MnIj(PMe3)2], which has a trigonal bipyramidal five-coordinate structure, with axial phosphines (at Mn—P = 2.43-2.44 A). Undoubtedly the latter compound is but the tip of the iceberg , and we can expect to see a considerable further development of this area of Mn " chemistry although it is pertinent to recall that the phosphine alkyls of Mn " disproportionate. 

Typical reactions are amine and phosphine alkylations or additions to a carbonyl group (Scheme 4.3). In these examples, because of the development of dipoles in... 

Guino-o MA, Zureick AH, Blank NF, Anderson BJ, Chapp TW, Kim Y, Glueck DS, Rheingold AL (2012) Synthesis and structure of platinum bis(phospholane) complexes Pt (diphos )(R)(X), catalyst precursors for asymmetric phosphine alkylation. Organometallics 31 6900-6910... 

The gas-phase reactivity of proton-bound NHC-H-PCyj has been investigated. NHCs are shown to be more basic than PCyj, accounting for the [Ru]-NHC complexes to be more efficient than their PCy3 counterpart. Collision-induced dissociation was shown to result in phosphine alkylation, formation of methylimidazole, and elimination of cyclohexene. Activation of Hj by aminocarbenes has been studied computationally. The energy of every elementary chemical event of the process has been determined, with special attention given to substituent effects on the energy barriers. 

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