Phosphines mixed

Mixtures with calcium hydride or strontium hydride may explode readily, and interaction of the molten chlorate is, of course, violent. A mixture of syrupy sodium phosphinate ( hypophosphite ) and the powdered chlorate on heating eventually explodes as powerfully as glyceryl nitrate. Calcium phosphinate mixed with the chlorate and quartz detonates (the latter producing friction to initiate the mixture). Dried mixtures of barium phosphinate and the chlorate are very sensitive and highly explosive under the lightest confinement (screwed up in paper). 

K4Ni(CN)4 is a yellow solid which is extremely sensitive to oxygen and moisture. It can be prepared by reducing K2Ni(CN)4 in liquid NH3 with an excess of potassium17 and decomposes in water with H2 evolution. CN ions can be easily replaced by ligands with greater jt acceptor properties such as CO, NO and phosphines. Mixed carbonyl and nitrosyl cyano complexes have been prepared by direct reactions (equations 1 and 2).18,19... 

There are four comprehensive reference texts on phosphine coordination chem-istry. Two are somewhat out-of-date, but the article by Levason is more recent. However, all four give much useful information on synthetic procedures for the preparation of primary, secondary and tertiary phosphines diphosphines multidentate and macrocyclic phosphines mixed Group 15 donor and mixed Group 15/16 donor systems and phosphorus-containing heterocycles. The coordination chemistry of phosphorus has expanded to include P4 fragments, Pg rings, and even naked phosphorus atoms, for example, nine-coordinate P and -Pg systems. ... 

Attention should be paid to the fact that the ratio of Pd and phosphine ligand in active catalysts is crucial for determining the reaction paths. It is believed that dba is displaced completely with phosphines when Pd2(dba)3 is mixed with phosphines in solution. However the displacement is not eom-plcte[16]. Also, it should be considered that dba itself is a monodentate alkene ligand, and it may inhibit the coordination of a sterically hindered olefinic bond in substrates. In such a case, no reaction takes place, and it is recommended to prepare Pd(0) catalysts by the reaction of Pd(OAc)2 with a definite amount of phosphinesflO]. In this way a coordinatively unsaturated Pd(0) catalyst can be generated. Preparation of Pd3(tbaa)3 tbaa == tribenzylidene-acetylacetone) was reported[17], but the complex actually obtained was Pd(dba)2[l8],... 

The mixed triarylphosphine 787 can be prepared by the reaction of (trimethylsily )dipheny phosphine (786) with aryl halides[647]. Ph3P is converted into the alkenylphosphonium salt 788 by the reaction of alkenyl tri-flates[648]. 

Many of these reactions are reversible, and for the stronger nucleophiles they usually proceed the fastest. Typical examples are the addition of ammonia, amines, phosphines, and bisulfite. Alkaline conditions permit the addition of mercaptans, sulfides, ketones, nitroalkanes, and alcohols to acrylamide. Good examples of alcohol reactions are those involving polymeric alcohols such as poly(vinyl alcohol), cellulose, and starch. The alkaline conditions employed with these reactions result in partial hydrolysis of the amide, yielding mixed carbamojdethyl and carboxyethyl products. 

THP—Amide Process. THP has also been made directly from phosphine [7803-5-27] and formaldehyde. The THP so generated contains one less mole of formaldehyde than either THPC or THPOH. It can be used in a THP—amide flame-retardant finish. The pad formulation contains THP, TMM, methylol urea, and a mixed acid catalyst (93—95). 

In the presence of a large excess of PH, primary phosphines, RPH2, are formed predominantiy. Secondary phosphines, R2PH, must be either isolated from mixtures with primary and tertiary products or made in special multistep procedures. Certain secondary phosphines can be produced if steric factors preclude conversion to a tertiary product. Both primary and secondary phosphines can be substituted with olefins. After the proper selection of substituents, mixed phosphines of the type RRTH or RR R T can be made. 

If aromatic aldehydes or ketones are used, the tertiary phosphine product sometimes rearranges to a mixed phosphine oxide. 

Secondary phosphines are likewise intermediates in the syntheses of phosphonites. The primary and secondary phosphines can also be used to make other mixed phosphines. 

Primary Amyl Alcohols. Primary amyl alcohols (qv) are manufactured by hydroformylation of mixed butenes, followed by dehydrogenation (114). Both 1-butene and 2-butene yield the same product though in slightly different ratios depending on the catalyst and conditions. Some catalyst and conditions produce the alcohols in a single step. By modifying the catalyst, typically a cobalt carbonyl, with phosphoms derivatives, such as tri( -butyl)phosphine, the linear alcohol can be the principal product from 1-butene. 

Dimesitylimidazolium chloride in the presence of potassium tert-butylate reacts with [RuCl2(PCy3)2(=CHPh)] or [RuCl2(PCy3)2(=CHCH=CMe2)] to yield the mixed phosphine-carbene complexes [RuCL(L)(PCy3)(=CHPh)] or... 

In principle, the quaternization reactions are extremely simple the amine (or phosphine) is mixed with the desired haloalkane, and the mixture is then stirred and heated. The following section refers to the quaternization of l-alkylimidazoles, as these are the most common starting materials. The general techniques are similar, however, for other amines such as pyridine [9], isoquinoline [10], 1,8-diazabi-cyclo[5,4,0]-7-undecene [11], 1-methylpyrrolidine [12], and trialkylamines [13], as... 

Apart from Ru(CO)5 and other carbonyls, there are mixed carbonyl-phosphine species and a few simple phosphine complexes like Ru(PF3)5 and Ru[P(OMe)3]5 [61a]. 

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