Tertiary butyl phosphine

Arsine (ASH3) and phosphine (PH3) are extremely toxic, so less hazardous substitutes such as tertiary butyl arsine, C4H1 j As, and tertiary butyl phosphine, C4H11P, are being considered. 

Metallorganic chemical vapor deposition (MOCVD) is now widely used in the preparation of III-V and II-VI devices. In addition to the hydride gases used as source materials in other CVD systems (e g., arsine and phosphine), less toxic liquid alternatives (e.g., tertiary butyl arsine and tertiary butyl phosphine) are also used in MOCVD systems along with other toxics such as cadmium alkyls and mercuiy.[42][43]... 

The dihydrido complexes (Table 62) can be obtained by the oxidative addition of molecular hydrogen to rhodium(I) complexes (equation 186).10,119,922""926 The tri(f-butyl)phosphine complexes can be prepared either from the chlororhodium(I) complex,923 or rhodium trichloride.927 The former method seems more reliable since the latter reports the complex as a matt green substance, a color uncharacteristic of tertiary phosphine rhodium(III) complexes. Indeed, Masters and Shaw report that the related tertiary phosphines PBu2R (R = Et, Pr) give green rhodium(II) complexes in this reaction (see Section 48.5.2.1 above).268,269... 

Photoelectron Spectroscopy.—The spectra of the reactive methylidynephosphines (70 R = Ph, TMS) have been compared with the stable tertiary butyl compound. " The vertical ionization potentials of trimethyl-, methylphenyl-, and triphenyl-phosphines have been measured. The basicity order in the gas phase is the reverse of that in solution and of the basicity order of amines in the gas phase. " ... 

TADDOL a,a,a, a -tetraaryl-4,5-dimethoxy-1,3 -dioxolane TASF, Tris-(Diethylamino)sulfonium difluorotrimethyl silicate TBAF, Tetrabutylammonium fluoride TBDMS, tert-Butyldimethylsilyl TBS = TBDMS t-Bu, Bu, tert-Bu, Tertiary butyl TCPP, Tris(p-chlorophenyl)phosphine TDMPP, Tris(2,6-dimethoxyphenyl) phosphine... 

With aluminium hydride, reduction to a phosphine can be effected (6.58). Hydrolysis yields methylphosphonous acid which exists in the tautomeric methylphosphinic add form (6.164). Although this seems fairly general for RPX2 compounds, it appears that steric hindrance can prevent hydrolysis of the second P-Cl bond and the product is RPH (0)C1, when R is 2,4,6 tri-tertiary butyl benzene. 

Modifying the reaction medium to involve liquid ammonia with metallic lithium, f-butyl alcohol, and white phosphorus, to which is added the haloalkane, is reported to provide the primary alkylphos-phine derived from the haloalkane.19 Similar results are reported for the reaction of red phosphorus with sodium acetylides20 and by treatment of red phosphorus with sodium metal in an organic medium followed by the addition of two equivalents of f-butyl alcohol and the haloalkane.21 The latter approach is noteworthy in that moderate yields (45%) are obtained for primary phosphines derived from secondary haloalkanes (Figure 2.6). Mixtures of tertiary phosphines bearing one or two acetylenic linkages are produced in low yield ( 15%) by the reaction of lithium acetylides with white phosphorus in liquid ammonia followed by addition of a haloalkane.22... 

Aqueous two-phase hydrogenations are dominated by platinum group metal catalysts containing water-soluble tertiary phosphine ligands. The extremely stable and versatile N-heterocyclic carbene complexes attracted only limited interest, despite the fact that such complexes were described in the literature [62-65]. Recently, it was reported that the water-soluble [RuXY(l-butyl-3-methylimi-dazol-2-ylidene) ( 76-p-cymene)]n+ (X=Ch, H20 Y = C1-, H20, pta) complexes preferentially hydrogenated cinnamaldehyde and benzylideneacetone at the C = C double bond (Scheme 38.5) with TOF values of 30 to 60 h 1 in water substrate biphasic mixtures (80 °C, lObar H2) [66]. 

This addition proceeds more readily with the more electron rich 2.6-di-tert-butyl-4-methyl-X -phosphorin 109 b or 2,6-dimethyM-phenyl-X -phosphorin 109 c. The H-NMR signals are in accord with the proposed structure (Table 15). The resonance of the phospha-barrelene 110 a m benzene appears at 6 = + 65 ppm (H3PO4 standard) which corresponds to the resonance of tertiary phosphines. 

Strukul and co workers recently prepared a series of cis and trans isomers of the platinum- t-butyl peroxide complexes Pt(R)(OOBu )L2 (R = CF3, Ph, etc. L = tertiary phosphine). The X-ray crystal structure of the franx-[Pt(Ph)(OOBu )(PPh5)2] (88) revealed a square-planar arrangement with... 

In 1970 we showed that the tendency for cyclometallation of a tertiary phosphine ligand could be increased enormously by the presence of bulky substituents on the tertiary phosphine (1). Thus with Structure I, cyclometallation usually occurs and occurs rapidly to give Structure II if R = t-butyl(Bu ) if R = Ph, it either occurs less rapidly... 

In contrast to the tertiary amines, trialkylphosphines have strong donor properties and form exceedingly stable coordination complexes with a wide variety of metal salts such as those of univalent copper and gold, and bivalent platinum, palladium, and mercury.1 Like phosphine itself, many of these tertiary alkylphosphines are highly flammable, toxic, and extremely susceptible to air oxidation. Ease of oxidation first decreases and then increases as the alkyl group becomes larger.2 3,4 5 The n-butyl compound is thus a convenient member of this group for preparation. 

The parent TMM complex (190 R = H) undergoes photochemical ligand substitution with trifluorophosphine or trimethylamine Al-oxide assisted substitution with tertiary phosphines or t-butyl isocyanide (Scheme 5A) Trimethylamine A-oxide assisted substitution using isoprene as the incoming ligand results in C-C bond formation to afford the bis-TT-allyl complex (197). An intramolecular version of this reaction is also known.The parent complex (190 R = H) reacts with electrophiles. Addition of HCl or Br2 gives the methallyl complexes (192) and (198), respectively. Tetrafluoroethylene adds across the Fe bond to afford (199) under photochemical conditions. Complex (190) undergoes Friedel-Crafts-type acylation with... 

However, cyolopentadienyl and indenyl f-butyl isocyanide complexes have been obtained by the original method, that is, by heating CugO with hydrocarbon and ligand. Although Cu(i7-C5H5)(Bu NC) is undoubtedly isostructural with the tertiary phosphine complexes, the indenyl complex, Cu(indenyl)(Bu NC)3, is almost certainly tr-bonded on account of its infrared and NMR spectra to say nothing of its stoichiometry (303). 

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