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KP15 a New Potassium Polyphosphide.

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of the neopentane skeleton and P - C ~ H S groups[2,31. Both
compounds are readily soluble in THF or ethanol but
insoluble in benzene or petroleum ether.
\
I
.
Received: November 14th, 1966
[Z 378 IE]
German version: Angew. Chem. 79, 380 (1967)
Publication delayed at authors' request
('1 Dr. J. Ellermann
F. Poersch
Institut fur Anorganische Chemie,
Universitat Erlangen-Nurnberg
8520 Erlangen (Germany)
Fahrstrasse 17
[I] Part 6 of Spiro-heterocyclic Compounds. - Part 5: J. Ellermann and K. Dorn, Chem. Ber., in press. - We thank Prof.
H. Behrens for support of our work.
121 J . EIIernrann and K . Dorn, Chem. Ber. 99, 653 (1966).
[3] J. Ellermann and K . Dorn, J. organomet. Chemistry 6, 157
(1966).
[4] J. Ellermann and K . Dorn, Angew. Chem. 78, 547 (1966);
Angew. Chem. internat. Edit. 5, 516 (1966).
[S] H. Behrens, J . Ellermann, e f a ] . , unpublished.
161 K. Issleih and A.Tzschach, Chem. Ber. 92, 1125 (1959).
[7] C. B. Wooster and N . W . Mitchell, J. Amer. chem. SOC. 52,
688 (1 930).
181 F. S. Kipping and A . G. Murray, J. chem. S O C . (London) 1927,
2737
[9] G. Wilkinson and J. M . Birmingham, J. Amer. chem. SOC.76,
4821 (1954).
[lo] H. P. Fritz, Advances organomet. Chem. 1, 280 (1964)
KP,,, a New Potassium Polyphosphide
By H . G. von Schnerin: and H. Schmidt [ * I
After a detailed study of the reaction conditions in the system K!P, red needles of a compound could be prepared
that had been observed previouslyrl-41 but had not been
accurately characterized. Elemental analysis and determination of the structure showed that it was potassium
polyphosphide KP15.
Preparation and Properties: Potassium and red phosphorus
are heated at 650 OC in a sealed quartz ampoule (length 20 cm;
temperature gradient 650,000 "C); the yield depends on the
K : P ratio, 5 to 20 atoms-% of K being favorable; traces of
water favor the deposition appreciably (chemical transport by
way of phosphines?). KPls is deposited at 300-320°C as
transparent, ruby, flat needles; it is odorless and is stable indefinitely in air. It is not attacked by H 2 0 and only slowly by
concentrated oxidizing acids. Samples are decomposed for
analysis by bromine-nitric acid in a sealed tube at 120 O C .
Strucfure: KP15 crystallizes in the triclinic form [a = 23.74,
b = 9 . 6 9 , c = 7 . 2 1 A , 0r=116.7*, @ = 9 7 . 5 " , y=90.0°;
space group Pi ;Z = 41 withmarked twinningparallel to (100).
Studies of single crystals show the structure contains phosphorus units in the form of infinite tubes,unidimensional along
[OlO], of pentagonal cross-section, and divisible into Pi5
units (see Figure). Of the 15 P atoms only one is bound to two
other P atoms ()Pa), the others being bound to three other P
atoms (>P). Each potassium atom unites four (P1& units to
each other, so that a two-dimensional framework parallel to
(100) results. Each potassium atom has 6 near neighbors (2 P<
at 3.48A; 4 P< at 3.24 or 3.37A). If these linkages are also
taken into account, then the PIS unit contains P atoms linked
in three different ways: (I) KlPLK, (11) K-Pf, (111) :P<; (I)
and (11) have a tetrahedral and (111) a pyramidal structure. The
P-P distances are 2.18 to 2 . 3 0 A ; the bond angles at the
phosphorus are between 93 and 112 O . If the peculiar relation
of (I) to the K-P distances [d(K-P<) > d(K-PO1 is
considered, the view that K+ and Pi5 ions exist becomes
tenable.
The structures of KP15 and of HgPbP14[ll (here P( I S
replaced by Pb and one P-P bridge is missing) shows that PS
units play a part i n such polyphosphides (see Figure). Men-
356
tion should also be made of the compounds KPlo"] and
T1P5[51, whose structures are not yet known. Thurn and
Krebs [61 have demonstrated recently that such tubular phosphorus units are in fact structural elements of violet phosphor us.
Received: January 2nd, 1967
[Z 410 IE]
German version: Angew. Chem. 79, 323 (1967)
[*I Prof. Dr. H. G. von Schnering
and Dip].-Chem. H. Schmidt
Anorganisch-Chemisches Institut der Universitiit
Hindenburgplatz 55
44 Miinster (Germany)
[I] H. D . Korte, Dissertation, Universitat Munster, 1960.
[2] G. Gnutzmann, F. W . Durn, and W . Klrmm, 2. anorg. allg.
Chem. 309, 210 (1961).
[3] H. Krebs, K. H . Miiller, I. Pakulla, and G. Ziirn, Angew.
Chem. 67, 524 (1955).
[4] H. Krebs, and Th. Ludwig, Z. anorg. allg. Chem. 294, 257
(1958).
[5] H. Puff, H. Spender, and H . Gotta, Naturwissenschaften 53,
405 (1966).
[6] G. Thurn and H. Krebs, Angew. Chem. 78, 1101 (1966);
Angew. Chem. internat. Edit. 5, 1047 (1966).
Stability of Aminal Esters and their Reactions
with Aromatic Aldehydes
By H . Bredereck, G. Simchen, H . Hoffmann, P . Horn, and
R . WahlI*l
Since the synthesis of bis(dimethy1amino)methoxymethane
( l a ) "1, we have prepared further aminal esters ( I ) (2-41 by
treating N,N,N',N'-tetramethylformamidinium methyl sulfate [ ' I with sodium or potassium alkoxide (molar ratio 1:1)
in ether or cyclohexane at room temperature. After filtration
and distillation of the solvent under vacuum, the aminal
esters ( I ) were obtained. Their purity was established by
N M R spectrometry.
M=Na,K
(1)
R
( l a ) CH3
( I b ) CzHsCxH,
( l c ) iso-CSH,
( I d ) t-C4Hg
I
Yield (%)
62
60
45
68
[I1
[2]
121
[3,4]
Content of ( I ) in
equil. mixture (%) [a1
62-64
62-66
54
32-33
Angew. Chem. internat. Edif. 1 Vol. 6 (1967)
f No. 4
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