Triphenylphosphite complexes

The titanocene monocarbonyl-triphenylphosphite complex, Cp2Ti-(CO)[P(OPh)3] (46) has also been prepared by this method (50). The cyclopentadienyl protons of 46 appeared as a doublet (/h p = 2.5 Hz) 46, while the parent ion (m/e = 516) was found in the mass spectrum. 

N. K. Kochetkov, L. I. Kudryashov, and A. I. Usov, Interaction of diisopropylidene-glucose with halogen-triphenylphosphite complexes, Dokl. Akad Nauk SSSR, 133 (1960) 1094-1097. 

It has already been shown that the nitration with nitric acid in acetic anhydride provides the general way of obtaining /V-ni trohctcrocyclcs. As an alternative synthesis of the aforementioned compounds, and, in particular, 1-nitrobenzotriazole, the reaction of 1-chlorobenzotriazole with the silver nitrate-triphenylphosphite complex can be suggested [273],... 

Scheme 7. The catalytic reaction mechanism of trans-1,4 polymerization of butadiene with the bis(triphenylphosphite) complex [Ni(7 -RC3H4)(P(OPh3)2]PF6 as the catalyst.

These cfs-complexes were shown to have latent behavior they were inactive at room temperature in model olefin RCM and CM reactions, as well as in enyne metatheses [60], yet the catalytic activities became very high when the reactions were carried out at 80 °C in toluene [60, 61]. Triisopropylphosphite and triphenylphosphite complexes led to the most active catalysts, the former being faster. In addition, both cis- and trans-NHC-phosphite catalysts were found to... 

More than half of the members of this family have been structurally characterized and the Au-C distances correlated with the donor ability of the /rchemical shifts of 13C resonances in the NMR spectra. According to these results, the /rcarbene ligand appears to be comparable to that of triphenylphosphite P(OPh)3. Owing to the bulkiness of the lBu substituents, the complexes are not aggregated in the crystals. By contrast, the corresponding methyl-substituted compounds are aggregated to form chains via aurophilic contacts and are photoluminescent.18... 

There are many phosphine and phosphite complexes of iron(O), sometimes acting as P,C-donors in orthometallated complexes. In general this area is deemed to be organometallic chemistry, so we shall cite just one recent reference to act as a possible point of entry to this area, relating to [Fe(CO)2 P(OPlfi3 P(OPh)2(OC6Fl4) which contains both a P- and a P,C-donor triphenylphosphite ligand. ... 

The photochemistry of these aryl complexes has been briefly investigated by Nesmeyanov and co-workers (98,98a) and is quite similar to that of the analogous alkyl complexes. Irradiation of CpFe(CO)2Ar complexes in the presence of tertiary phosphines at room temperature led to the formation of the corresponding monosubstituted derivatives (98) [Eq. (96)]. Prolonged irradiation in the presence of triphenylphosphite... 

DEHALOGENATION Diiron nonacarbonyl. Lithium amalgam. Phenanthrcnc-Sodium. Sodium thiosulfate. Triethyl phosphite. DEHYDRATION Alumina. Boron trifluo-ride n-butyl etherate. Dimethyl sulfoxide. Hcxamethylphosphoric triamidc. Iodine. Methyl N-suIfonylurethanc tricthylamine complex. Phosphonitrilic chloride. Thio-nyl chloride. Triphenylphosphite methlo-dide. 

The coupling reaction between phenol and ethylene to give ortho-ethylphenol is catalyzed by (triphenylphosphite)ruthenium complex [20]. In this reaction, the ortho C-H bond of triphenylphosphite is cleaved by orthometallation, and then insertion of ethylene followed by reductive elimination lead to the formation of triarylphos-phite having an ortho-ethylphenoxo group. Transesterification between the phosphite and phenol then releases (ortho)-ethylphenol by reproducing triphenylphosphite (Scheme 14.8). 

A similar complex was observed on mixing triphenylphosphite with acrylonitrile although, in spite of its formation, polymerization did not ensue 239). Hence, the following mechanism was proposed for the initiation by the trietylphosphite ... 

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