A Comprehensive Treatise on Inorganic and Theoretical Chemistry

27O INORGANIC AND THEORETICAL, CHEMISTRY
F. Hoffmann, and L. Tschugaeff and I. I. TscherniaefE prepared platinous
dichlorohydroxylaminoammine, [Pt(NH3)(NH2OH)Cl2], by boiling in a flask
with a reflux condenser, platinous c*s-dihydroxylaminediamminochloride with
sufficient dil. hydrochloric acid to dissolve the salt in the cold ; when the hot soln.
is cooled, the salt separates in yellow crystals. L. Tschugaeff and I. I. Tscherniaeff
reported platinous hydroxychlorohydroxylajiiine, Pt(NH2OH)Cl(OH), but
F. W. Pinkard and co-workers could not confirm this.
L. Tschugaeff observed that complex hydrazine compounds can be prepared
without difficulty if water be excluded, and he obtained platinous tetrahydrazinochloride,
[Pt(N2H4J4JCl2, by adding hydrazine to a soln. of platinous tripropylammoniumchloride
[Pt{(C3H7)3N.HCl)2Cl2], in chloroform ; and L. Tschugaeff
and M. Grigorieff prepared it by interaction of hydrazine hydrate with substances
of the type [Pt(SC2Hg.C2H4-C2H5S)2Cl2J, or of [Pt(R2S)2Cl2]. The chloride can be
kept for several days in the dry condition, but decomposes more rapidly in aq. soln.
especially on the addition of alkali, with effervescence and liberation of platinum.
With sodium iodide soln., the chloride gives a precipitate of the iodide,
[Pt(N2H4)4JI2 ; whilst potassium platinochloride soln. produces a flesh-coloured
precipitate. It forms platinous tetrahydrazinochloroplatinite, [Pt(N2H4)4]PtCI4;
and platinous tetrahydrazinohydrochloride.
L. Tschugaeff and M. Grigorieff prepared platinous trans-dihydrazinediamminochloride,
[Pt(NH3)2(N2H4)2]Cl2, by adding 4 to 6 c.c. of hydrazine hydrate
to a gram of dry platinous £raws-dichlorodiammine, the temp, rises a little, and as
soon as al 1 is dissol vcd an excess of alcohol is added. The oil which separates soon
crystallizes, and the product is then washed with absolute alcohol, followed
by dry ether. The product is dried a short time in air and finally over
phosphorus pentachloride. The colourless acicular crystals are more stable
and less soluble than the corresponding cis-salt. It gives a precipitate with
potassium iodide ; and a red precipitate of platinous dihydrazinodiamminochloroplatinite,
[Pt(NH3)2(N2H4)? JPtCl4, which soon darkens, is formed when
the soln. is treated with potassium chloroplatinite. Hydrochloric acid in the
cold forms a stable and sparingly soluble platinous /m/v*-dihydraJzinediamminodihydrochloride,
[Pt(NH3)2(N2H4)2JCl2.2HCl.
IJ. Tschugaeff and M. Grigorieff prepared platinous cis-dihydrazdnediammino-
Chloride, [Pt(NH3)2(N2H4)2JCl2, by the action of hydrazine hydrate on platinous
cis-dichlorodiammine, as in the case of the trans-salt. The cis-salt furnishes
colourless, prismatic crystals, which can be preserved for a few days, but gradually
darken owing to liberation of platinum ; the soln. in water, which dissolves
large quantities of the solid, decomposes much more rapidly. The mol. conductivity
of a soln. of a mol of the salt in 250 litres of water at 25° is 236-6. Other salts
of the new complex were prepared by double decomposition of the chloride in
concentrated aq. soln. with potassium iodide and with potassium platinochloride,
the precipitate in the latter case being greenish. The addition of hydrochloric
acid to an aq. soln. of the chloride causes the deposition of a much
less soluble, crystalline platinous ^Ig-flibyflraM^^fliftirimiTioflihyflrofil'iloride,
[Pt(NH3)2(N2H4)2 |C12.2HCl, which, on treatment in aq. soln. with potassium
chloroplatinite furnishes platinous **-riiliyfli^Mrif^iftiirimino. K. Drew and H. J. Tress obtained platinous quaterethylamlnocWorldo,Cl
> tetn4]Cl8.2HaO; platinous quaterethylaminoehloroplatinlte,[Pt etn4]PtCl4; platinous
dichloroquaterethylaminochloroaurate, [Pt etn4Cla]AuCl5 ; and platinous quaterpropylamino-