2282

Notes

dissolved in 20 ml of 5 N acetic acid, was reduced by slow addition of 40 ml of 100 vol. hydrogen
peroxide; the solution was boiled to decompose the excess of peroxide and then the preparation was
completed according to the standard method [6].
Solutions of known weights of the heacyanochromate(ll 1) were passed through the ion-exchange
column; variable results, with no sharp end-points, were obtained on potentiometric titration. A
solution of the complex acid decomposed in the dark into cyanide-free chromium(Ill) hydroxide and
hydrocyar.ic acid; no chromium could be detected in the solution by oxidation with persulphate, from
which it was inferred that the equilibrium constant for the decomposition reaction (1) was at least 10s.

Acknowledgement-This work was carried out during study leave from the University of Karachi.
The author thanks Dr. A. G. Sharpe for useful suggestions and discussion, and is also grateful to the
Ministry of Education of the Government of Pakistan for the award Of a Central Overseas Training
Scholarship and to the University of Karachi for granting study leave.

UniversityChemicalLaboratory
Cambridge, England

A . M . QURESHI*

*Present address: Department of Chemistry, University of Karachi, Karachi 32, West Pakistan.

J. inorg,nucl.Chem.,1969,Vol.31, pp. 2282 to 2284. PergamonPress. Printedin Great Britain

The t~B nuclear magnetic resonance spectra of some cyclic boron e s t e r s

(Received 21 October 1968)
THE IIB RESOr~^NCEof a boron ester is in general a broad featureless line. We have examined the ~1B
resonances of a series of cyclic esters of phenylboronic acid and of various dialkylaminoboronic
acids having five- and six-membered ester rings, with the following observations. Linewidths of
400-1000 cycles were noted for many of the esters (Table I) but for certain six-membered rings,
including all of the dialkylaminoborinans, the signal was too wide for meaningful measurement. The
chemical shifts of the neat esters (relative to methylborate) appeared to be diagnostic for ring size,
12-13 ppm downfield for phenylborolans, 6-8 ppm downfield for dialkylamino borolans, and 8-9 ppm
downfield for phenylborinans. When solutions of phenylboronates in coordinating solvents were
studied, it was found that HB resonance lines were narrowed considerably with increasing dilution,
but there was only a slight narrowing for the dialkylaminoboronates (Table I ).
Acyclic esters of phenylboronic acid with aliphatic alcohols have chemical shifts intermediate
between those of five- and six-membered ester rings. The five-membered ring signals appear at lowest
field which may signify least shielding of the boron nucleus. It has been suggested that neat liquid
phenylboronates are associated[ I, 2] through oxygen bridges to relieve ring strain, rendering the boron
four-coordinate and by inference more shielded. Here the six-membered rings show more shielding
than acyclic esters, and these more than five-membered rings, a finding in conflict with other evidence
[ I, 2] that association decreases in the order 5 > 6 > acyclic esters, so some other factor, e.g. intramolecular rr-back donation from oxygen may also govern the chemical shifts. Back-donation is more
likely in the six-membered rings which could accommodate a 120 angle a! boron strainlessly. The
effect of acetonitrile, a coordinating solvent in which a considerable drop m tLmperature occurs on
mixing, is merely to narrow the signals and not to shift them, thus in dilute solution ,;:e boron is
apparently no more shielded than in the neat liquid. For borolans, boron may well be tetrahedral in
both environments. The line-narrowing may be due to viscosity effects, or to some rapid exchange of
boron between two sites (associated borolan or 7r-bonded borinan ester and acetonitrile-ester complex)
with fortuitously identical chemical shifts. It is noteworthy that the dialkyl-aminoborolans, which
are probably associated through nitrogen rather than oxygen bridges[3] do not show ~ substantial
1. A. Finch and P. J. Gardner, J. chem. Soc. 2985 CI964).
2. A. Finch, P. J. Gardner and E. J. Pearn, Trans. Faraday Soc. 62, 1072 (1966).
3. R. H. Cragg, J. inorg, nucl. Chem. 30, 395 (1968).

Notes

2283

Table I

JiB nmr spectra. Chem. shifts relative to external (MeO)3B in ppm

(a) Variation in ring size.
Compound*

Conc. in CH3CN

Chem. shift.

12.5%

12.9

11

10

12.3

111
IV
V
VI
V 11

10

12.8

10
10
10
N o resonance observed
at any dilution

- 12.5
-8.4
-8.4

O---C Hz

(b) 2-Dialkylamino- 1,3,2- Dioxaborolans

N--B

R
Compound
R=R'--Me
R=R'=Et
R=R'=nPr
R = R' = iPr
R=R'=nBu
R = Me, R' = Ph
R = Et, R' = Ph

VIIi
Hz

Chem. shift
-6.5
-6.6
-6-9
-6-7
-6-5
-7.5
- 8.0

(c) Variation with concentration

Compound*
Conc. in CH.~CN
!
100%
I
50

-width (cps)
500
165

Chem. shift
- 12-5
-

12-4

25

83

12"9

12-5

66

12.9

100
50
40
30
20
100
50
25
-

855
115
100
95
80
132
94
74
-

V
V
V
V
V
V I I I , R = R' = nPr
V I I I , R = R' = nPr
V I I I , R = R' = nPr
PhB(OEt)2

--8'0
- 8"5
-8"5
- 8-5
- 8"5
-6-9
-6.8
-6-8
-- 10-4

*Key. Cyclic phenylboronates derived from diols 1 ethane-1"2-11 propane

-1:2-, I l l butane-2:3-, IV pinacol, V propane-1:3-, VI butane-l :3-, V I I pentaerythritol.
t C h e m . Shifts for neat compounds are very inaccurate (probably 1 ppm) since
the lines are so broad, but for more dilute solutions the error may be _+0-2 ppm.

2284

Notes

narrowing effect. Probably there is little or no coordination between acetonitrile and these esters.
Mooney and co-workers[4] have proposed that the difference in chemical shift between free and
complexed boron be taken as a measure of complex strength, in this criterion the acetonitrile complexes of phenylboronates would be very weak if they exist.
EXPERIMENTAL
Phenylboronates [5] and dialkylaminoboronates [3] were prepared as previously reported. HB nmr
spectra were measured relative to external emthyl borate as standard on the A.E.I.R.S.2 instrument.

Acknowledgement- We thank Mr. J. W. Akitt for measuring some "B spectra.

University of Kent at Canterbury
Inorganic Chemistry Department
University of Newcastle upon Tyne NEI 7RU

R . H . CRAGG
J . C . LOCKHART

4. P.G. Davies and E. F. Mooney, Spectrochim. ,4cta 21, 1445 0965); 22, 953 0966).
5. A. Finch andJ. C. Lockhart, J. chem. Soc. 3723 (1962).

J. inorg,nucl.Chem.,1969.Vol.3I, pp. 2284to 2288. PergamonPress. Printedin Great Britain

Decay

of 77raGe

(Received 12 November 1968)

THE DECAY of nmGe has been studied by several investigators[l,2,3]. But there is a rather big
discrepancy among the reported data on, for example, its half life. This is believed to be mainly due to
the fact that by a Nal(TI) detector the 158 keV 3" rays of 77raGe could not be sufficiently resolved from
the 138 keV y rays of 7SmGe. Also, when,8 rays of 77raGe were followed to determine its half life,/3 rays
of Tsm'WGeand/or 77SGecould have brought some errors into the determination.
EXPERIMENTAL
Enriched 7eGe (93.55%) oxide was reduced by hydrogen into metallic powder and irradiated for
I-2 min in the Kyoto University Reactor (KUR) using the pneumatic system. (The neutron flux was
about 5 x 10n n/cm= sec.) Within 1min after the irradiation, y rays from the irradiated source were
observed by a 2cc Ge(Li) detector connected to a 1024-channel TMC pulse height analyser. The
resolution of the detection system was 2.1 keV in FWHM for the ~a~Ba 3, rays. The maximum
dead time of the system was about 10% and all the countings were carried out by live time setting. In
order to check the accuracy of the clock and the dead time readings of the analyser, an accurate stopwatch was also used side by side.
After following the decay of nmGe by the Ge(Li) detector, the source was subjected to chemistry.
Within 30 min after the end of irradiation, TTAs, the daughter product of 77raGe, was separated from
other products and its 240 keV and 250 keV 3' rays (the sum of the intensities per disintegration is
2.0% [3])were observed by a 3" x 3" Nai(Tl) detector connected to a 400-channel pulse height analyser.
The chemical separation of As from Ge and Ga was done as follows:
The irradiated Ge metal target was dissolved in the (HF + HzOD solution and the As(V) carrier and a
small amount of Nal solid were added. Then, the solution was saturated with H=S gas and the precipi1. W. S. Lyon and J. S. Eidridge, Phys. Rev. 107, 1056 (1957).
2. J. B. van der Kooi and H. J. van den Bold, Nucl. Phys. 70, 449 (1965).
3. Nuclear Data Sheets, Nuclear Data Group. Printing and Publishing Office, National Academy
of Sciences - National Research Council, Washington D.C. 25 (1966).