Titanium phosphine hydride

DIENES Bcn/.yldtlotobis(Iriphenyl-phosphine)palladium(ll). Copper(I) bromide-Dimethyl sulfide. Palladium(Il) chloride. Tetrakis(triphenyEphosphine)-palladium. Titanium IVichloride-Lithium aluminum hydride. 

Potassium phosphinate, 4453 Sodium disulfite, 4802 Sodium dithionite, 4801 Sodium hydride, 4438 Sodium hypoborate, 0164 Sodium phosphinate, 4467 Sodium thiosulfate, 4798 Sulfur dioxide, 4831 Tetraphosphorus hexaoxide, 4861 Tin(II) chloride, 4064 Tin(II) fluoride, 4325 Titanium trichloride, 4152 Titanium(II) chloride, 4111 Tungsten dichloride, 4113 Vanadium dichloride, 4112 Vanadium trichloride, 4153 Zinc, 4921... 

Monocyclopentadienyltitanium phosphine complexes have also been prepared and reviewed previously. The formally divalent titanium precursor, (r/s-CsI Is)Ti(dmpebCl, serves as a synthon for the corresponding methyl and hydride compounds, ( 5-CsI Is)Ti(dmpe)2k (R = Me, H), which are diamagnetic and crystallographically characterized.57 Addition of ethylene to these compounds results in formation of 1-butene, 3-methyl-l-pentene, and... 

IODINE (7553-56-2) A powerful oxidizer. Material or vapors react violently with reducing agents, combustible materials, alkali metals, acetylene, acetaldehyde, antimony, boron, bromine pentafluoride, bromine trifluoride, calcium hydride, cesium, cesium oxide, chlorine trifluoride, copper hydride, dipropylmercury, fluoride, francium, lithium, metal acetylides, metal carbides, nickel monoxide, nitryl fluoride, perchloryl perchlorate, polyacetylene, powdered metals, rubidium, phosphorus, sodium, sodium phosphinate, sulfur, sulfur trioxide, tetraamine, trioxygen difluoride. Forms heat- or shock-sensitive compounds with ammonia, silver azide, potassium, sodium, oxygen difluoride. Incompatible with aluminum-titanium alloy, barium acetylide, ethanol, formamide, halogens, mercmic oxide, mercurous chloride, oxygen, pyridine, pyrogallic acid, salicylic acid sodium hydride, sodium salicylate, sulfides, and other materials. 

ALKENES Calcium amalgam. N,N-Dimethylformamide dimethyl acetal. N,N-Methylphenylaminotriphenyl-phosphonium iodide. N,N,N, NrTetra-methyldiamidophosphorochloridate. Titanium(O). p-Toluenesulfonylhydra-zine. Tii-n-butyltin hydride. Triphenyl-phosphine-Diethyl azodicaiboxylatc. Trityl tetrafluoroborate. 

While the connection between the structure of the hydrides and their pyrophoric behavior seems to be obscure, it should be pointed out that the compounds of hydrogen fall into three distinctive groups the above-described phosphines, silanes, and boranes, which have covalent bonds the salt-like hydrides of the alkali and alkaline earth metals and the interstitial, nonstoicbiometric or berthollide —type hydrides of the transition metals—e.g. the rare earths, titanium, and zirconium. Pyrophoric compounds are found in all three groups. 

Lemaire et al. developed a catalytic system for the reduction of secondary phosphine oxides to obtain secondary phosphine boranes using titanium(iv) isopropoxide as eatalyst and tetramethyldisiloxane as hydride source, giving excellent yields. ... 

Aside from the titanium-mediated process described above, the asymmetric addition of aUcyl groups to aldehydes can also be performed by nickel catalysts. This traces back to seminal work of Fujisawa et al. who had found that the addition of AlMc3 to aldehydes can be catalyzed by Ni(acac)2 and is strongly accelerated by phosphines and phosphites [50]. Racemic additions to aromatic and aliphatic aldehydes thus occurred in good yields with as little as 0.1 mol% of nickel. Interestingly, the reaction with AlEt3 and Al(/Bu)3 predominantly led to the respective addition products with only small amounts of the reduced primary alcohols. This is in contrast to the nickel-catalyzed 1,4-addition of higher aluminum trialkyls to enones, in which the rate of p-hydride elimination surpasses that of 1,4-addition [51]. 

---