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PF3, (CH3)3SiCl -> (CH3)3SiF, and RC(O)Cl -> RC(O)F. Others
include the conversion of (C6H5)3P into (C6H5)3PF2 and of
(R3NC(S)S)2 into R2NCF3, R=alkyl. In organic chemistry, fluorides
are easily accessible from alcohols, geminal fluorides RR'CF2 from
the respective aldehydes or ketones, and acyl fluorides RC(O)F from
carboxylic acides by using DAST. Because DAST is easy to handle and
gives clean reactions in syntheses, this Gmelin volume devotes much
space to the description of the chemical and physical properties od
DAST.
The present volume describes acyclic Sulfur-nitrogen compounds with
sulfur of the oxida- tion number II. The first chapter deals with
sulfur imide (S=NH), N-organyl-sulfur imides (S=NR, R = or- ganyl),
and metal complexes of sulfur imides. N-Organyl-sulfur imides have
not been isolated, but they can be trapped, for example, by
cycloaddition and stabilized by coordination to transi- tion
metals. 11 The following chapter present a detailed survey of other
8 -N compounds with one- coordinate sulfur, e.g., dithionitrous
acid (S=N-SH) and derivatives, the salts of the dithionitryl ion (1
+) ([S=N=S]+), and N-thionitroso-diorganyl-amines (S=NNR , R =
organyl). Only the reac- 2 tions of [S=N=S]+ AsF5, among the known
[S=N=S]+ salts, have been extensively studied. Cycloadditions with
alkenes and triple bonded compounds produce 1 ,3,2-dithiazolium
salts and their derivatives. S=NN(CH )z and S=NN(C H )z form
transition metal complexes. The 3 6 5 Iigand is coordinated via the
S atom in a monodentate manner.
The present volume describes organoberyllium compounds containing
at least one berylli um-carbon bond, except the beryllium carbides
and cyanides. It covers the literature com pletely to the end of
1986 and includes most of the references up to mid-1987. This
Gmelin volume is different from all other volumes of the series on
organometallic compounds in that it is dedicated to an area of
research which has virtually come to a complete standstill.
Organoberyllium chemistry has never been a very popular field, and
only few workers have contributed to its slow growth, as is seen by
the relatively small number of publications in the field. This very
modest development became stagnant in the early 1970's and was
followed by a rapid decline. This exceptional fate of a branch of
organometallic chemistry is only partly due to the very limited
number of potential application~ of beryllium and its compounds.
The compounds of this element are, in principle, at least as
interesting and intriguing to scientists as those of other metals
in the Periodic Table. No doubt the main reason for the apparent
ban of all experimental organoberyllium chemistry is to be found in
the established, and alleged, hazardous properties of beryllium
compounds. Although similar hazards have been established for other
organometallics where active research is still in process, e. g. ,
mercury and lead, these observations were absolutely lethaI for
organoberyllium research.
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