Proceedings of the 8th International Conference on Coordination Chemistry: Vienna, 7.–11. September 1964

474 Pages·1964·19.245 MB·English

by  Ekkehard Fluck, Werner Kerler, Wolfgang Neuwirth (auth.), V. Gutmann (eds.)

PROCEEDINGS
of the
8 INTERNATIONAL CONFERENCE
th
ON COORDINATION CHEMISTRY
Vienna, 7. - 11. September 1964
Edited by
V.GUTMANN
Technical University of Vienna
Springer-Verlag Wien GmbH
ISBN 978-3-7091-3652-2 ISBN 978-3-7091-3650-8 (eBook)
DOI 10.1007/978-3-7091-3650-8
Paper 6B1 has been substituted by the following paper:
6 B 1
THE ADDUCT OF NITROSYL FUJORIDE WITH PHENYLTETRAFWORO
PHOSPHORANE - NEW FLUOROPHOSPHATES.
R. Schmu tzler and G.S. Reddy
E.I.du Pont de Nemours and Co •• Inc •• Wilmington/Delaware. U.S.A.
Nitrosyl fluoride reacted with phenyltetrafluorophosphorane in FREON
113 .) (b.p. 46.6°) ort preferably. FREON 12 .) medium (b.p. -30°)
between -80 to 00 to give a light orange. solid 1 : 1 adduct [0. [IJ is stable
below 00• but undergoes a sudden irreversible decomposition at ca. 100 with
formation of undefined. purpie products. NOF thus cannot be recovered
directly from the adduct. The result of an F19 NMR study of [IJ was not
conclusive. due to its sensitivity both towards moisture and heat. Indirect
evidence for the formulation of [I] as a nitrosyl salto NO+CsHsPFs- was
obtained from some of its reactions.
The formation of phenylphosphonic acid upon hydrolysis of [IJ shows that
the phenyl group remained unchanged during the reaction of C6HlF" with
NOF. Reaction 0([1] with BFa in nitromethane gives NOBF" and C6HlF". the
latter was found to be unaffected by BFa:
[I] + BF
3
The following reactions. typical of nitrosyl compounds of type [I] were
also observed:
[I] + ROH < 00 • RONO
< 00 •
[I) + ArNH ArF
2
< 00
[I] +R~H~ R~·NO
The latter reaction js particularly interesting and was studied in most
detail with respect to the formation both of the nitrosamine and a novel
type of fluoro complex. [C6l\PFs]-' obtained as the dialkylammonium salto
The following stoichiometry was established for the reaction of [I] with
secondaryamines.
----------
.) Registered trade mark. E.I.duPont de Nemours and Co •• Inc.
(+) ( -)
~N·NO + I\NH2 CsHsPFs
A number of the new fluorophosphates could be obtained as stable products,
sufficiently volatile to be distillable or sublimable in a high -vacuum.
The following reaction provided a particularly easy route to salts con
taining the [R(Ar)PFs] - anion, which were isolated in high yields, along
with alkyl( aryl) -dialkylaminotrifluorophosphor anes,
(+) (-)
..... 00
1 R(Ar)PF.. + 2 I)NH ---+~ R(Ar)PF3NI) + I)Nf\ R(Ar)PFs
A phenylpentafluorophosphate, together with a novel cationic species,
also resulted from the isomerization of phenyldimethylaminotrifluoro
phosphorane. It occurs when the fluorophosphorane is allowed to stand at
room temperature,
The plI NMR spectrum of the ion [RPFs] - consists of a doublet of
partially overlapping quintuplets. The observed pattern is consistent with an
octahedral structure, four fluorine atoms occupying equatorial sites, and one
being in axial position. Most indicative as to the nature of the fluoro anion
is the p3I chemical shift, e.g. of[C6HlFsr: its very large positive value
(+ 136 p.p.m.) suggests a highly shielded phosphorus atom, comparable to
=
PF6- (op + 143,7 p.p.m.). p19 NMR spectra are also consistent with the
above formulation of the anions, [RPFsr.
Both, plI and FI9 NMR spectra of alky1(aryl)-dialkylaminotrifluoro
phosphoranes may be interpreted in terms of a trigonal bipyramidal model
with the dialkylamino - and organic hydrocarbon group occupying equatorial
sites.
The reaction of nitryl fluoride with phenyltetrafluorophosphorane is
different from that of nitrosyl fluoride. Instead of formation of an adduct,
nitration of the aromatic nucleus takes place. Hydrolysis of the product gives
the known p-nitrophenylphosphonic acid, suggesting that nitration occurred
largely in p -position to the -PF. . group.
8 A 2 has been substituted by the following paper:
8 A 2
NQR SPECTRA AND S"TRUCTURE OF TETRACHLOROAURATES(lII).
V. C ag li 0 t i , G. S art 0 r i and C. F u r la n i
Istituto di Chimica Generale e Inorganica,
Universita di Roma, Italy.
Nuclear quadrupole resonance spectroscopy is a very promising novel
technique for the study of coordination compounds. Its applicability includes
observation of quadrupolar nuclei of central metal atoms Ce. g. 21 Al, 59 Co,
t
63Cu, 6SCU, 11SIn, 193Ir, 191Au, etc.) as weH as of ligand nuclei 4N, 3S,37C},
'I9Br, 81Br, 1271, 1SAS, etc.), but the former possibility has been very little
explored untU now. Instrumental difficulties, namely poor versatility of NQR
spectrometers and practical non availability of commercial apparatus have
probably retarded the diffusion of NQR technique in the field of coordination
chemistry, but vistas are now quite encouraging: e. g. unpaired electron spins
do not prevent detection of NQR lines, and Mössbauer effect measurements can
be complementary to NQR spectroscopy for nuclei which are quadrupolar only
in excited states.
NQR data yield primarily informations on the p electron densities in the
valence shells, from which the net resulting charge on the investigated atom
can be easily inferred by me ans of some simple models, e. g. of the TOWNES
DAILEY theory. Usually the accuracy of experimental measurements is rather
high, and is at present not matched by equally powerful and accurate inter
pretative theories. Therefore at this initial state of application in the field
of coordination chemistry we are devoting more attention to the experimental
results of NQR spectroscopy, their immediate interpretation and their close
connection with X -ray structural data.
NQR of ligand halogen nuclei in halo -complexes has been reported first
by ITO, NAKAMURA and KUBO far several hexacoordinated complexes of
transition elements (I), wh ich possess almost invariably regular octahedral
structure and exhibit therefore often only one halogen resonance line. Square
plan ar halo-complexes have been much less thoroughly investigated, except
MeldX4 (2) and Me PtX. (2,3), which have again only one resonance fre
2
quency, and have therefore presumably regular square planar structure.
We have investigated salts of the [AUCl.r anion which is roughly but
not exactly square planar [also [AuBr.]- is distorted square (4)] givillg there-
fore a more complex NQR spectrum (see also reference (5) ).
Especially in the sodium salt very close agreement is obtained between
NQR (two resonance lines) and X-ray data (two non-equivalent types of
chlorines in the [AUCI4] unit).
The chlorine coupling constant is rather high, and a simple interpretation
following the TOWNES -DAlLEY scheme indicates acharge of about -0,4 per
chloririe. Although we cannot distinguish between effects of s - or d -hybridiz
ation, of ionic bonding and '/I' -bonding, the observed high values are strongly
suggestive of a high degree of covalency of the coordinative bonds which is
in line with the very high optical electro-negativity reported for Au (III).
NaAuC~. 2 H20, rhombic prisms, space group Pmna, contains planar
[AUCI4] units, with three long (2,27 Ä) and one short (2,22 A) Au-Cl bonds.
Long-bonded chlorines are relatively elose to Na+ ions (3,0 - 3,2 Ä), where
as the short -bonded chlorine is not less than 4,4 Ä from the nearest 50dium.
r
We have therefore two types of non-equivalent chlorines in each [AUCl
4
unit (6).
Ammonium chloroaurate is not isomorphous with the sodium salti
preliminary X -ray data seem to indicate monoelinic structure with presumably
lower microsymme°try of the [AuCI4] - unit.
NaAuCl .2 H as microcrvstalline powder has two 35CI resonance lines
(27,36 and 248 ,33 2M c/sec at 25J0 ). Both frequencies have a slightly negative
temperature coefficient; e.g. values of 27,81 and 28,76 Mc/sec are observed at
-1400•
Below -140°, a sudden reversible shift to 28,8 and 29,3 Mc/sec i5
observed which suggests that asolid state transition is taking place. The
average of the frequencies observed, at room temperature is consistent,
according to the TOWNES -DAILEY model and assuming 150/0 s -hybridization,
with a charge distribution of +0,61 e on Au and -0,40 e on Cl.
Potassium chloroaurate has again two frequencies (26,75 and 27,36 Mcl
sec at 180), whereas ammonium chloroaurate has four frequencies in the
ranges 26,62 - 26,98 - 27,43 - 27,62 Me/sec, which indicate presence of
four sets of chemically non -equivalent chlorine atoms in the crystal.
References
1. NAKAMURA, D •• KUBO, M., ITO, K •• and cow •• J.Am.Chem.Soc ••
82, 5783 (1960) and -84, 163 (1962); Bull.Chem.Soc.Japan, -35, 518 (1962)
-
and 36, 1056 (1963); Inorg.Chem., ~, 61 and 690 (1963).
2. ITO, K., NAKAMURA, D., KU NITO , Y., ITO, K., and KUBO, M.,
J.Am.Chem.Soc •• 83. 4526 (1961).
3. MARRAM, E.P •• McNIFF, E.J •• and RAGLE, J.L •• J.Phys.Chem •• 67,
1719 (1963).
4. COX, E.G •• and WEBSTER, K.C •• J.Chem.Soc. (London), 1936, 1635.
5. lEGEL, S. L• • and BARNES, R. G •• Catalog of nuclear quadrupole inter
actions and resonance frequencies in solids - U. S. A.E. C., I, 520 (1962).
6. BONAMICO, M., DESSY, G• • and VACIAGO, A• • Unpublished results.
8th INTERNATIONAL CONFERENCE
ON COORDINATION CHEMISTRY
Organised by
VEREIN OSTERREICHISCHER CHEMIKER
Sponsors :
INTERNATIONAL UNION OF PURE AND
APPLlED CHEMISTRY
DER BUNDESMINISTER FüR UNTERRICHT
DER BÜRGERMEISTER DER STADT WIEN
President of the Conference:
H. NOWOTNY, Vienna
Executive Committee:
V. GUTMANN, Vienna (Chairman)
A. MASCHKA, Vienna (Secretary)
E. HA YEK, Innshruck
H. MALISSA, Vienna
O. POLANSKY, Vienna
U. WANNAGAT. Graz
Thia Conference has heen supported partially hy the
United States Government
througb its European Research Office, Rheingau Allee 2, Frankfurt (M), Germany, and through the
Bundesministerium für Unterricht
Wien I, Minoritenplatz 5
PIENARY IECTU RES
(to be published in the Journal
of Pure and Applied Chemistry)
Ho HARTMANN. Frankfurt/Main (Germany): .. Neue Ansätze in der Theorie
der Komplexionen und ihre physikalische Begründung" •
J.IEWJS. Manchester (UK): "Metal-Metal-Interactions in Coordination
Compounds".
E.L.MUETTERTIES. Wilmington/Delaware (USA): "Tetrahedral and Octa
hedral Cationic Chelates of the MaiD Group Elements" •
F.G.A.STONE. Bristol (UK): "The Role of Organometallic Compounds in
the Development of Coordination Chemistry" •
J.A.SYRKIN. Moscow (USSR): ·The Nature of Bonding of Water Moleeules
in Crystallohydrates and Clathrates· •
A. A. VLCEK. Prague(CSSR): ·lntermediates of Electroreduction of Transition
Metal Complexes· •