Reactions trimethylphosphine adduct

More recently, this group has explored the reactions of metal atoms with a variety of radicals that have also been formed by discharge methods. In the later studies, compounds such as CF3HgSCF3 (94), (CF3)2Ni, and (CF3)2Pd were prepared, the last two being isolated as the trimethylphosphine adducts (95). 

A single uranium halide adduct of a monodentate phosphine has been reported reaction of UCI4 with excess PMcs permits isolation of the trimethylphosphine adduct, UCl4(PMe3)3. ... 

Alkene complexes of Ti, Zr and Hf have been intensively investigated with regard to the nature of bonding and the close relation to olefin oligomerization and polymerization. Alkene complexes of zirconocene and hafnocene are isolated as the trimethylphosphine adduct, Cp2M(T -alkene)(PMe3) (33) [92-94]. Cp 2Ti(CH2=CH2) (34) is a 16 electron ethylene complex with a rich reaction chemistry as summarized in Scheme 6.4 [95-99]. The reaction profile of 34 indicates that the metallacyclopropane canonical form makes an important contribution [100]. 

The trimethylphosphine adduct, (MeCp)3Ce-PMe3, has been prepared by reaction of (MeCp)3Ce(THF) with PMe3 in diethyl ether and recrystallized from diethylether at... 

In contrast, reaction of a THF solution containing a mixture of the rhodium isomers 79b and 80b with trimethylphosphine in the dark consumes only the 1,2,3,6-q isomer 80b to give the new PMe3 adduct 83 (169). The... 

X-ray diffraction provides a structural analysis of the adduct obtained between acetone and triethylphosphine (155) in the presence of bromine. The process of obtaining 155 is an acid-catalysed process, while the adducts obtained in the presence of chlorotrimethylsilane may be ascribed to neutral attack of the nucleophile leading to the zwitterionic complex, as shown in Scheme 46. In Scheme 46 triethylphosphine may be substituted by trimethylphosphine. When triphenylphosphine or tributylphosphine were used, no reactions were observed, owing to the reduced nucleophilic power of the bulky phosphines and to the insolubility of the obtained adducts. 

The first disilene-group-4 metal complex, disilene-hafnium complex 240, is synthesized using a similar reaction to those shown in Eqs. (108) and (109) [Eq. (113)].153 The reaction of 240 with trimethylphosphine gives the phosphine adduct 241 [Eq. 

Behrens and Wilke (77) have described a method for resolving enantiomeric Homer phosphines (PR Rs) by complexation with tj3-(+)-(l/ ,5/ )-pinenyl nickel bromide dimer a 1 1 adduct is formed, purified by recrystallization, and the optically pure phosphine released by reaction with excess trimethylphosphine. The geometry of the adduct 32 formed by methyl-ferf-butylphenyl phosphine is shown here. The, 3C-NMR spectrum... 

Leahy et al. have found that using tributylphosphine instead of amines can significantly accelerate the MBH reaction of propionaldehyde with methyl acrylate, and avoid the undesired formation of aldol products that are often generated in amine-catalyzed MBH reaction at room temperature, to afford the corresponding adduct in good yields (Scheme 2.95). Trimethylphosphine and l,4-diphosphabicyclo[2.2.2]octane, the phosphorus analog of DABCO, do not catalyze the addition of propionaldehyde to methyl acrylate. ... 

Trimethylphosphine is a ligand of proven utility in oiganometallic chemistry. However, because of its expense when purchased from commercial sources (Strero Chemicals) or its poor to moderate yidds when isolated as the silver iodide adduct [AgI(PMe3)l4, its potential is not fully realized. Frequently, large quantities of the phosphine are required, for example, as a reactive solvent or in the field of lanthanide and actinide chemistry, wherein the lability of the phosphine ligand may require crystallization from neat tri-methylphosphine. Similar considerations apply in exploratory synthetic early transition metal chemistry. In transition metal ylide chemistry, access to quantities of PMea is also very desirable, particularly when excess ylide is required. The volatility of PMe3 facilitates work-up of reaction mixtures and... 

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