Hydrides organic derivatives

Phosphorus compounds exhibit an enormous variety of chemical and physical properties as a result of the wide range ia the oxidation states and coordination numbers for the phosphoms atom. The most commonly encountered phosphoms compounds are the oxide, haUde, sulfide, hydride, nitrogen, metal, and organic derivatives, all of which are of iadustrial importance. The hahde, hydride, and metal derivatives, and to a lesser extent the oxides and sulfides, are reactive iatermediates for forming phosphoms bonds with other elements. Phosphoms-containing compounds represented about 6—7% of the compound hstiugs ia Chemical Abstracts as of 1993 (1). 

In a manner similar to OsH(OH)(CO)(P Pr3)2, the hydride-metallothiol complex OsH(SH)(CO)(P Pr3)2 adds Lewis bases that are not bulky such as CO and P(OMe)3 to give the corresponding six-coordinate hydride-metallothiol derivatives OsH(SH)(CO)L(P Pr3)2 (L = CO, P(OMe)3). OsH(OH)(CO)(PiPr3)2 and OsH(SH)(CO)(P Pr3 also show a similar behavior toward dimethyl acetylenedi-carboxylate. Treatment of OsH(SH)(CO)(P Pr3)2 with this alkyne affords 6sH SC(C02Me)CHC(OMe)6 (CO)P Pr3)2, which is the result of the tram addition of the S—H bond to the carbon-carbon triple bond of the alkyne. Phenyl-acetylene, in contrast to dimethyl acetylenedicarboxylate, reacts with OsH(SH) (CO)(P Pr3)2 by insertion of the carbon-carbon triple bond into the Os—H bond to give the unsaturated alkenyl-metallothiol derivative Os ( )-CH=CHPh (SH) (CO)(P Pr3 )2, the inorganic counterpart of the organic a, (3-unsaturated mercaptans (Scheme 46).92... 

During the past 15 years data from experiments with different types of animal tissues and micro-organisms, using intact cells, crude extracts or purified enzymes, have firmly established the general occurrence of nucleotide reductases and have stressed their importance for DNA synthesis in essentially all types of rapidly growing cells [54]. It has been proposed that ribonucleotide diphosphates lose a hydroxide ion from C-2 to form a carbonium ion which is then stero-specifically reduced by a hydride ion derived from thioredoxin [54]. Adenosine diphosphate and guanosine diphosphate (as well as uridine and cytidine diphosphates) are reduced in this manner. 

Derivatives of these hydrides, including organic derivatives, are named using the rules of substitutive nomenclature, or by using coordination nomenclature, as seems more appropriate. 

Carbon is, of course, unique in the number of hydrides it forms, but the elements in the proximity of carbon in the Periodic Table have a similar, if more restricted, propensity to form hydrides. Silicon, germanium, boron and phosphorus are obvious examples. For hydrides of these elements, and especially for their organic derivatives, the methods of substitutive nomenclature can be applied to obtain suitable names. 

A. C. Bond, K. E. Wilsbach, and H. I. Schlesinger The Preparation and Some Properties of Hydrides of Elements of the Fourth Group of the Periodic System and of their Organic Derivates. J. Amer. chem. Soc. 69, 2692 (1947). 

Silicon is the most plentiful electropositive element on the earth s crust, being three times as abundant as aluminum and six times as abundant as iron. Yet the only compounds of silicon which have been important to human history are those natural forms of silica and the silicate minerals which are used in the building arts and in ceramic technology. Only within the past 90 years have hydrides and organic derivatives of silicon been synthesized, and the chlorides 30 years before up to a few years ago it could be said that all these substances were still relatively unknown products of the laboratory, unimportant save for their scientific interest. The chemistry and technology of silicon continued to be dominated entirely by consideration of the inorganic silicates. 

Apart from organic derivatives of pentazene, N5H5, the cyclic compound 78 is, so far, the only other Group IV derivative of this hydride (35). It is formed by the action of ethyl nitrite on the silylated lithium hydrazide 77 in diethyl ether at -78 C [Eq. (99)]. It is a colorless crystalline... 

Compounds in which hydrogen is bonded to the alkali and alkaline-earth metals except beryllium are prepared by direct synthesis from the metals or amalgams. Beryllium hydride is prepared by pyrolysis or reduction of organic derivatives. 

Organic derivatives include alkyl and aryl phosphines such as triphenyl phosphine (C6H5)3P. As with the hydrides these compounds are much less basic than the corresponding nitrogen compounds... 

In the processes described above a silicon halide, ethoxide, or hydride is brought into reaction always with an organic derivative of another metal however, a Si-C bond can also be formed by treating a silylmetal compound, e.g., (triphenylsilyl)-potassium308 or -lithium309 with an aryl or alkyl halide, thus ... 

NH3 NHj, azane (parent hydride name), amine (parent name for certain organic derivatives), trihydridonitrogen ammonia NHj", azaniumyl, trihydridonitrogen) 1 +) -NHj azaniumyl ammonio azanuidyl, trihydridonih ate( 1—) NH, ammine... 

NA H3NNH3, diazane (parent hydride name), hydrazine (parent name for organic derivatives) NHNHj, diazan-2-ium-l-ide H3NNH3, diazaniumyl, bis(dihydridonitrogen) O N-N) 1+) hydraziniumyl H3N=NH3, diazenediium HjNNHj, diazane, hydrazine "NHNHj diazan-2-ium-l-ido... 

Koski et al have studied the use of pyrolysis followed by the use of thermal conductivity cells for the determination of deuterium in deuterated boron hydrides, their organic derivatives and nitrogen compounds. The volatile boron compounds were first... 

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