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Heavier alkali metals annual survey covering the year 1975
133
HEAVIER
ALKALI
ANNUAL
SURVEY
METALS COVERING
THE YEAR 1975
EDWIN M. KAISER Department 65201
of
Chemistry,
University
of
Missouri,
Columbia,
Columbia,
Missouri
(USA)
COilTENTS 1.
Physical
2.
Synthetic
Aspects
3.
Reactions
with
4.
References
PHYSICAL
1.
Organic
Chemical
Inorganic
the
of
with
lithium-formaldehyde
of
I [l]-
also
by differences
Kinetic sodium
have
Annual
These
do not
certain
which
results
with
ion-ketyls
bonding
led
Survey
the
authors
coverinq
to
the
not
pair
the
149
where
studies conclude
year
1975
in
of
contrkst
YO SCF
one minimum correto
those
two stablezspecies
explanations
ion-pairs.
by an -ab initio
presence
only
earlier
and solvation,
and conductometric
has been studied
suggest
are
ion
agree
sodium in
ion pair
results
to
scopy
145
Compounds
1
sponding
but
and Organometallic
ORGANIC CHEMICAL ASPECTS
UHF procedure,
exist.
133 113
The sodium-formaldehyde
the
Aspects
of
concerned
The discrepancies
obtained the
ion-pair
with
spectro-
are
reconciled
respectively.
on ethereal that
the
solutions carbanion
see J.Oryanome:al.Chm.,
of is
polystyryl-
a naked
one and
133(1375)1-38-
131
that the cation Na(DME)*+(II)
in dimethoxyethane
(DME) can be described
by the kinetic
entity
; s
[Z]-
II
papers described
Several
phosphino,
acidities
functional
groups
often
a rough guide
give
carbanion
as tentative,
[3]_
at best.”
the gas phase [4]. species
to carbanion derived
and other
earlier
establishment metric
cussed.
pKa values Indicators
measurements
are ascribe-1
delocalized.
Many earlier of certain available
nitriles
of acidities
kinetic
acidi ties
regarding
rela-
must be regarded
in DPlSO
charge
in these
of the above two papers
paper which describes
the
in DMSOusing a spectrophoto-
pKa’s have now been changed and
compounds as a function to cover
same
and ketones
to the negative
The results
assigned
and compared
those of the same compounds in
ones are summarized in a full
method [5].
different
and even approach
scale
conclusions
of several
thio,
by these
‘*_ _ .at though
stabilities,
The acidities
of an absolute
activated
that
from kinetic
Such results
being extensively
have been determined
conclude
of car-
sulfonyl-contafning
carbon-acids
The authors
have been found to parallel
of certain
molecules
of several
stabilities
work in the area of acidities
acidities
and phenyl-substituted
with the kinetic
tive
additional
Thus, equilibrium
bon acids.
of solvent
the pK range of 8.3
are dis-
to 30.6
in DMSOare
listed. Another group of workers has presented
experimental
of a large
number of anions
derived
from carbon,
DMSO[6]-
Both charge delocalization
and steric
said
to affect
i
the solvation
The trifluoromethylsulfonyl
oxygen,
solvation
enthalpies
and halogen
hindrance
acids
to solvation
in
are
energies. group has been found to lie
between the nitro
135
and benzoyl tion
groups
in its
ihe use of
[7]_
ability
this
and other
and cyclopropyl
isopropyl, an estimate
moieties
to be made of
and thus destabilized.
have also and other
a variety
of substituted
dithianes
unrelated
study,
that of
the kinetic
tritiated
stabilize
and acyclic
conjugative been studied
of
III
indicating
substantially
are strained it
is concluded
with carbanions.
using cesium salts
in cyclohexylamine
acidity
data which allow
systems,
effect
ioniza-
to methyl,
anions
compounds in !lMSO[S],
triphenylmethane
carbanions
quantitative
to which cyclopropyl
a large
of hydrocarbons
groups attached
has provided
Eoth in the cyclic
Equilibrium-acidities
rt-hydrogen atoms towards
functional
the extent
that the S02CF3 group exerts
variety
to activate
and a
and cesium salts
[9]_
Finally,
has been found
in an
to be greater
that alpha-trimethylsilyl
and
than
qroups
[IO]. (=5i)3C3H III
The bridgehead
hydrogen H3, shown in structure
IV, has been found to under-
go exchange
in deuterated
methanol using sodium methoxide
temperature
of 25” [ll].
In contrast,
conditions. authors side
to state
of bridged
enolates
results
ihese
Hl in IV fails
along with those on other
that enolate
stability
chain
low
to exchange under these ring
systems have led the
in such polycyclics
is enhanced at the
boat forms but not at their
in locked
at the remarkably
forms is diminished
bows.
The stability
of similar
considerably.
IV
In
contrast
to
the
corresponding
non-phenylated
systems
V and VI,
the
rl-
c
136 hydrogens of VII and VIII are exchanged with deuterium rate suggesting
that
delocalization The results
the phenyl groups
from C4 to the double are discussed
at virtually
the same
in VII cause the elimination
of charge
bond at C6,7 previously
in relation
to earlier
observed
described
carbonium
in V [12]. ion
chemistry.
The influence
viewed [13]_ tunneling distribution orientation latter
of
ionic
association
Other papers in this
in the elimination
reactions
are noteworthy
reactions
area have addressed
of five
reactions
VIII
in B-elimination
of certain
from E2 reactions of similar
P
VII
VI
V
(j-J’”
a”
0
0
Z-phenylethyl secondary
the question systems
alkyl
in that such eliminations
of hydrogen
[14].
tromides
of Z-butyl-N.N-disulfonimides
hris been re-
the olefin
[15-j, (IX)
afforded
and the [16].
only
The l-
butene.
‘Y RSOR I N\SOZR IX A new type of conversion reactions specifically
1.3-dehydrohalogenation
of species presumably eliminate
like
has been proposed
X to XI effected
proceed
by potassium
via ring-opened
potassium
chloride
intermediates
to afford
to account
r-butoxide
for
[17].
XII which stereo-
trans-products.
the The
__..-_
_r._..
_.
.
..-.
138 In conjugation
100 MHz [243. the authors is
with the NMRspectra
that the proportionality
conclude
of
cation,
phenyl tropyllum
constant
10 ppm/uni t charge
of
open to question. Conformational
mobility
annulene has been studied are interpreted bonds leading
zation
sequence
The cyclodecatrienyl
A full tion
at a higher
and by proton
scopy.
compound undergoes
Such topomeri-
field
abstraction indicates
directly
&positions
rather
than via a Interestingly,
of 5000-G. by reaction
of XX by potassium the presence
electrocyclization
of fenchone
and sodium pyrene
by CIDHP at 60-G [26].
paper appeared which discussed
at the five
toponers.
nine
temperatures
about the neighboring
anion XVIII has been prepared
of the homoenolization
occurs
at various
sodium anthracene,
as evidenced
The NMRspectrum of XVIII at -65” this
between
has been found to occur
such CIDW is not observed
species;
The spectra
chemically.
ttio alcohols
XIX with potassium
of cis,cis,cis,trans-[9]-
of the trans-bond
of sodium naphthalene.
disproportionation
salt
N+iR[25]-
to a dynamic equilibrium
Protonation or
by proton
in terms of rotation
is demonstrated
with water
in the potassium
triene
amide [27].
of a symmetricai
at -41°.
the results
(XXI) [28].
was demonstrated
of
of a detailed That deuterium
examinaexchange
by 13C and ‘H NMRspectro-
_ .
L
139
Other papers describing included
13C NMR of
the following:
LL’9], ‘ii RI!.? of
alky!malonates S-ketoesters
NMRexperiments
hydrocarbon
of
are treated
anion of a nydrocarbon
of
above technique
and the
39 K NMRand a7Rb
species
in the presence
electron
is a %nction
to investigate
to study electron
and its
parent
1361,
of such systems
transfer
exchanges.
peculiarities
transfer
of certain
which
It has
is a function
ihree
The processes
other
oapers
used the
in systems XXII where n = 3 and
between N-n-butylphthalimide
and to investigate
chains
between the aromatic
of n and temperature_
they were bimolecuiar
have been
by XXII (n = 3 to 20) [34].
the ESR spectra
intramolecuiar
4 1353.
phthalimide
inorganic
and
on one end and the corresponding
end as illustrated
in turn,
as if
[31].
Finally,
the dynamic flexibility
that the shape of
which,
5-diketones
as measured by ESR spectroscopy
to investigate
the freqilency
moieties
processes
on the other
been deter;?ined
[32]_
on certain
diethyl
of certain anion
compounds
[33]_
transfer
a radical
of several
the oxanonatetraenyi
have been effected
chosen as a tool
and related
the sodium salts
adduct of a carboxamide
of dibenzo-18-crown-6 Electron
of carbanions
the sodium enolates
the ‘l-l NMRof
[30],
‘H ?c?R 01 an alkoxide
contain
NMRspectra
electron
transfer
radical
anion
in XXII where Ar =
[37]. Ar_CCHZ-fiArL XXII
The following
benzyl c39.
[38],
toluene
radical
401, mesitylene
radical
anion
[41],
radical
have been prepared
species
2.3-naphthobarrelane
phosphinyl)ethylene radical
anions
silyl-aniline5 RcfcrrncBp. :19
radical
1433,
phane derivatives
radical
[44], [45.
radical anions anions
and radical
46, 473.
anion [40].
[38,
39, 403.
several
of certain anions
e-
recorded:
benzene radical
2.3-naphthobarrelene
anion [41], [42],
ESR spectra
and their
radical
anion
anion
and trans-1.2-fi(diphenylhindered
triptycene
of a variety
alkylbiphenyl and [2.2]-paracyclo-
of ring
substituted
140 Ultraviolet
spectroscopy
evidence
for
tions
potassium
of
only
attributed this
carbanion
carbanion
or
kinetics
of
with
lithium
the bleached
papers
a variety
in this
solvent
methoxide
or of
the effect
of
though solu-
exhibited
the spectra
that state
the excited persisting
by the relative
spectra
from solutions
potassium
state
tightness
of
fluoradenide
ion pairs.
THF and dioxane
longer
the authors
Second,
the hydrogen of
area
of
spectroscopy
of N-sodioamino-N-heteroaromatics
in the amino forms
the presence
Specifically,
[48].
UV
on the
effected
behaved
by
differently
in THF than in dioxane. of
the aggregates
in
media.
spectroscopy;
that
ions,
direct
from disodiotetraphenylethylene
It was found
were rationalized
Two other
XXIV [SO]_
free
the first
suggested the presence of contact
photoejection
[49]_
the respective
exist
bonded,
to obtain
in this
been used to study
in the two solvents,
First,
fluoradenide
18-crown-6
electron
These results
in methanol
tetramethylamnonium
has also
a 530-nm pulse
pairing
to hydrogen
in the presence of spectroscopy
ion
has been employed
conclude like
microwave
exchange
base
that
XXIII,
proceeds
not in the tautomeric
via
between a a-ally1
brief
mention.
have been studied
in the crystalline
spectroscopy
reaction
deserve
state,
such comoounds
imino forms as
has been employed propylene
in
to demonstrate
and deuterated
intermediate
by infrared
DHSO in
[Sl].
0) i;+ I
XXIII
Concerning continued of
mechanistic
to be studied.
sodium biphenylide
determining
studies, The current
on cis-stilbene
step was the conversion
anion [52].
-_
-.
the isomerization investigation
where it of the cis-
of ewas centered
was determined
to trans-stilbene around
the use
that
the rate-
to the trans-stilbene
radical
141 TWO
papers
more
aromatic
with
radical
were reacted
anions -
with E-hexyl
clude
that the irreversible
state
with little
The second various
paper studied
etherealsolvents
to that
differences
in shapes of potassium,
P-chloroquinoline
anions
are described
reactions
with E-hexyl
These authors
radical
suggest
plots
enolates
XXV provided
of iodobenzene
Fragmentation
con-
transistion [53].
carried
that the negative
out in charge
of fluorides
rela-
paper discusses
the
in both papers.
are subjected
with this
and related
products
the authors
have been found to react
the reactions
Another paper concerned
and anthracene
fluoride
The latter described
halides
on the halide”
in such reactions anion.
alkyl
an early
delocaliration
the Arrhenius
chemistry [56].
“involves
and charge
but not lithium
[55].
similar
among others,
transfer
is more localized
to afford
photostimulation
thiolate
similar
of the naphthalene
Several
describes
electron
of certain
sodiumnaphthalene
bromide and chloride;
[54]-
state
the reaction
In the first,
bond breaking
in the ttansistion tive
describing
appeared
with
to
SRNl mechanism
compounds with certain
of intermediate
radical
anions
and rationalized.
xxv The term ERCl has been applied chain elimination
process
XXVI with XXVII to afford
to a unimolecular
as illustrated styrene
radical
anion-radical
by the light-stimulated
derivative
XXVIII [57].
Several
reaction
of
other
examples are included.
e-02N-C6H4
NO2
XXYI An alternative
mechanism for
the acyloin
condensation
has been presented
112 which
does not involve
sists
of
a series
of
a-diketones discrete
steps
XXIX-XXX1 illustrate
Structures
0"'
Instead,
[SS].
differing
only
?R'
three
?R'-
R-C-0-$R
the pathway proposed
one from the other of
the suggested
con-
by one electron_
intermediates.
; ?- ?' R-C=CR
R-C-O-CR 0-
xxx
XXIX
Reduction
of XXXII with potassium
C&S]_
These results
rather
than phenylated systems_
I
has been shown to afford
are in marked contrast
0
cyclononyl
xxx1
to similar
XXX11
which previously
Possible
mechanisms are
of
ketone
proposed
varying
depending
presumably
arise
cerned with the formation that species
like
for
of
have been reacted base
XXXIV
to give
of substrates
via aryne
intermediates.
of benzofurans
like
with several
products
upon choice
XXXIV are intermediates
hZ1n
the current
reaction.
Ph
enolates
in the presence
products
of alkylated
xxx111
chlorobenzenes
yields
XXX111
have been shown to afford
xxx11
A variety
reductions
FPh *_ ‘H
-
dianion
like
XXXVII where it
in their
*Z)n
xxxv
XXXIV-XXXVII
and base [60]. A second
formation
dialkylaminoin
Most of
the
paper was con-
is demonstrated [61].
; :
143
1,4-Rearrangement alkali
metals,
protonation. than
ion
has been
XXXVIII,
prepared
realized
[62].
1,2-rearrangements
could
not
from
to afford
and NMR spectroscopy
related
Evidence
of
and
be garnered
the
XXXIX
This
corresponding
as evidenced
1.4-migration
increases
to demonstrate
in
the
the
much less
Li<
presence
and
by carbonation,
is
order
chloride
of
facile CS.
non-classical
XL.
e-Ph-C6H4C(Ph)2(CH2)3M
Ph2!
(CH2)3C6H4-@‘h
XXXVIII
XXXIX Ph XL
Other of
the
studies
Stevens
and axial
Favorskii
reaction <
2.
SYNTHETIC ASPECTS A warning
about
organornetallic
chloryl safer
References
route.
p_ l-l9
deserve
include
mention
a quantitative
sigmatropic of
of
CIDNP study
pathways
in
3-(I;-haloacyl)indoles
certain
another
has been
dichlorinated
explosion
published
benzocyclobutene.
fluoride.
that
the
[66],
the mechanism
in
latter
the
[6S].
Favorskii
The desired
[69].
potassium
perchloryl
of and
[68].
fluoride
The current
explosion
t-butoxide.
n-butyllithium,
3-fluorobenzocyclobutene
base-
[67],
methylketones
involving
latter
reactions
2-bronobenzo[6,7]bicyclo[3_2_l]-act-6-en-3-one
the
of
[63].
and forbidden
rearrangements
equatorial
a mixture
rearrangements
rearrangement
1641 , allowed catalyzed
of
and an
occurred
has been
with
and perprepared
by a
c--
-
._--
..
-.
--
- - -_
144 Another described
strong
[70]
internal
to
propargyl butoxide group
potassium
and employed
terminal
(XLI.
the
XLII.
The reactions
that
are
of
facile
[70.
G = 0,
KOH to afford
R [72]_
in
acetylenes
compounds or
base,
contrathermodynamic
713.
N,
5)
XLIII,
3-aminopropylamide.
In another
have
been
or
XLIV
postulated
to
isomerization
study,
reacted
proceed
a variety
with
depending
has been
via
of
potassium
upon the diallene
of
base
-bis-
tand
the
intermediates.
= --R
xQ
XX
XLIV XL111
Metalation addition XLVI
of
(37%)
is
oxide
by trimethylsilypotassium
has been
found
to afford
followed
a mixture
of
by
XLV (28%)
and
[733.
synthesis
illustrated
3-methyl-l-butene
ethylene
Several their
of
new,
stable
being by the
cyclobutadienes
proton
abstraction
conversion
of
XLVII
have
been described.
by strong to XLVIII,
bases
[74].
the
last
step
The process
of
--
145
Double dehydrobromination addition C7S] -
of
dimethylamine
The authors
of
XLIX
has been
suggest
that
by potassium
found
the
to give
reaction
t-butoxide
followed
6-dimethylaminofulvene
proceeds
via
m-benzyne
by (L)
LI.
XLIX
Cyclopropane zation
of
disilazane
and cyclobutanone
chlorocyanohydrins Similar
[76].
aminocyanoepoxides
like
[77].
of
The subject
(n
= 2 or
cyclizations LIII
ring
Other cyclizations
781.
LII
cyanohydrins
have
to afford size
in
3)
such
been prepared by cycli-
have effected
been
by sodiohexamethyl-
carried
pyrrolidines
like
cyclizations
out
on certain
LIV
(G = NH, 0 or
H2)
has been discussed [77.
described in 1975 include the preparation of epoxides
from B-hydroxyalkylselenonium salts
[79] and of naphthyridines from dinitriles
[801-
PR Cl (CH2),CHCN
/
0
G
CN
Ar
Ar
ii
LII
4
LIII
LIV
Alkylation convenient
and subsequent
synthesis
of
oxidation
chain-extented
of
LV has been
and a-branched
found
a-amino
to constitute acids ; several
a
146
_
examples are listed
[81]. ‘:
(RS)2~=~-c~-~02c2bi5
LV Cyclobutanones tuents
are readily
systems like described
containing cleaved
LVI or LVII,
by basic
hydroxide,
[82,
(1luY) to afford
and methyllithium
to give
v-substituted
reductive
The nucleophiles
group.
substi-
In conjunction
831.
the method represents
of a carbonyl
a lkoxide,
or 3,x-trinethylenedithio
reagents
respectively
spiroannelations,
geminal alkylation
u,u-dibromo
acids,
with earlier
alkylation used to date
esters,
or include
and ketones.
respectively.
-sJ/-\,
( 4’ Other studies
in this
area that deserve
of LVIII with non-enolizable rt-ketosulfones
(LIX)
carbonyl-containing nucleophile
versus
carbonyl
0
to afford
the generation
functional
to a vinyl
cyclopropanes tives,
[84],
aldehydes
halide
epoxides
mention
include
the condensation
enol ethers
by conjugate
and a discussion
from the reactions
of the formation acid
of a of deriva-
compounds, and base [86].
X
SO2R”
M’
-._.,G ----Nu LX
LVIII
covered
LX (G =
addition
of a-haloacrylic
R
Several
of hypothetical
of Darzens intermediates
group or cyanide) [85],
CONU
papers discussed
included
aliphatic
semidiones.
bicyclo[3_2_0]hep-2-ene-6.7-semidiones
Systems specifically [87],
cycloheptane-1.2-
..
-emidiones certain
[88],
alkenyl
carbocyclic
Finally,
and cycloalkyl
conjugated
%
substituted
unsaturated
the preparations
have been described
3_
.. __,. ._-_. ._ .._
1,2-semidiones
1,2-semidiones
of saphthalene
cesiun
[89],
and
[90].
and phenylpyridine
cesium
[91].
REACTIONSNITH INORGANICAND ORGAhOMETALLIC COMPOlJiIDS Eight examples of complexes
of alkali
retal
hydrides
potassium
eXalilDle.
similarly,
this
and metallic examole,
hydride
no reaction
and LX11 have been observed
with certain
hydride
cation
LX:
magnesium alkyls
and di-c-butylnagnesium
and diphenylmagnesiun
are important
in
was observed
determining
and aryls
afford
give
[92].
For
LX1 in benzene;
LX11 in ether.
which
in the case of
in reactions
complex
!ithium
60th sol-rent
is
hydride
formed;
for
and dimethyl-
magnesium in ether. !4Mg2R4ti
YMgR2H LX1
A revieir discussing published
[93].
LXII
certain
The synthesis
aspects and crystal
(CSHS)2Ee2C2SbH8> has been described polyhedral
expansion
chloride.
Metallocarborane
been
synthesized
transistion
been
[95].
including
atoms migrate
several
corresponding
novel
to adjacent
nickelaboranes
Tetraborane the
halides
[94]_
of
certain
titanium, close
has also
has been anion
deprotonated
[99]_
Some of
discussed
[97,
by potassium
The preparation
and vanadium have
Gth
their
rearrangements
vertices
of
[96].
by a
and ferrous
the mixed-metal
polyhedral
polyhedral been
zirconium,
carboranes of
has been
of a new ferracarborane,
The compound was prepared
Four isomers
thermal
chemistry
sodium cyclopentadienide
with
complexes of
structure
(CsV5)2CoNiCB7H8 have been prepared_
presented
metal
4.5C2B7H9
by treatment
metal
carborane,
of
of metallocarborane
sodium,
then
bimetallochemistry in
has
which
The synthesis
the of
983. hydride B5H8-,
or
ammonia
to afford
B6Hg-,
B5H12-,
B6H11-;
148
and B7H12 are above
also
species
treatment alkene
Mixed
_
of [rOO].
aluminium
with
their
novet
to certain
t complexes
has been
area
of
metal
of
LX111
the
metal
metal [tO7],
of
reviews
anions,
of metal
of
this
species
analog
carbonyl
and with
has been alkylated
and
Thus.
such species
aromatics L-1143,
[112],
and methyl
from
the by
an
fialcoholates to give
of
with
its
in
published the
discusses Grignard have alkali
C8K [lOB]_
syntheses
reagents
metai
base NMR
of
[105].
effected
by
amalgams
Sodium-amalgam
IV halides
proton
concerned
disodium
been
species
with
LXIV
reduction
which
[109].
[IOS].
has
Reaction
has given recorded
of
anion [llO].
(csH,)MO(cO),(~~~~,)~
LX111
of
of
several
been
use
anions
and Group
(csH,)M~(c0)2(c~~~3)~l
Reactions
have
review
carbonyls
alkyl
presence
Finally,
for
yields
cyclopentadienide
new isonitrite-containing
by a variety
the
high
borabenzene
their
pentacarbonyl[methoxy(phenyl)carbene]chromium(O) LXV;
in
reported
[lOZ].
Another
alloy
in
sodium
compounds [tO4]_
has afforded
been alkylated
with
and with
sodium-potassium
synthesized
[l Ol] _
presented
compounds
corresponding
been
hydride
[103].
preparations
the
sodium
reacted
carbonyl
been
have
derivatives
as a transition
Convenient
of
been
patterns
tetracarbonylferrate
with
have
reactivity
organometallic
treatment
with
n-cyclopentadiene
the
have
A new route
chloride
corresponding In
trialkytboranes
diatkylbromoboranes
(borinato)cobal of
NMR and “B spectra
described.
LXIV
metal have
carbonyl been
anions
interacted
fluoroolefins organometallics
[113]. [115].
the
have
been
subject
with
a-chloroenamines
1.2,3-tri-&butylcyclopropenium
of
several
[111].
papers.
fluorocation
149 Carbonyl
ferrate
ferrates
have
bony1
aldehydes [lli’],
[116],
and to
With
with
sandwich
[122].
with
uranium
11241
sandwich
Finally, to
it
nickel,
with
reduce
THF has
Primary
involving
benzene
Alvarino.
been
silicon
substituted
cyclized
niobium
[125]
have
papers
prepared
from
LXVI
has been
[128].
by bases
in
the
l,l’-
to afford
been
Dipentadienylzinc and zinc
from additions
LXVII
of
and LXVIII
Chem_.
[127].
[129,
mono- and have
been
1301.
R2pCH2CH2PR2’ LXVIII
and H-B.
Schlegel,
J_ Organomet-
chloride
various
LXVII
H_ Guerra.
sodium
complexed
derivatives
RPHCH2CH2PH2
Pedulli.
of
chlorotriisopropylgermane
vinylphosphorus
like
The ability
has been enhanced by complexing
pentadienylpotassium
to certain
cyclooctatetraene
disclosed_
[126].
synthesized
negatively
with
mention.
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salts
Several
and tantalum
deserve
Base-catalyzed
LXVI
J-H_
ferrocenes
carbon-halogen
polyphosphines
F. Bernardi. 6. 105 (1975) 711.
certain
de-
dipotassio-1,3,5,7-tetraphenylcycloocta-
stable
(i-C3H7)3GeNH2
2.
of
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phosphines
l_
stereospecific
[123].
disubstituted
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118.
Cooke,
Hagen.
Ann.
Anderson,
37 (1975)
and G.P.
(1975)
Liebigs J.
Hughes,
88
196;
342.
Organonet.
Chem.,
(1975)
Chem..
J_ Chem. Sot.,
Hodges,
87
86
Kalina,
Fischer,
Cyr,
Chem..
8 (1975)
D.G.
J_ Organonet.
Schubert
Inorg-
Chem. Res..
and E-A_
Angew.
Shul’pin,
J.
Chem.,
and A.A.
Chem..
Am. Chem. Sot.,
6863.
Lett..
Van Dyke,
Organomet.
J._ Organomet. J:
(1975)
Tetrahedron
and C.H_
J.
97
(1975) Organomet.
101
-
(1975)
Pogrebnyak,
97 (1975) 97
4009.
(1975)
C41. 6693.
i
- ..-
...- --._-
--
155
125.
C.
Elschenbroich
126.
G. Guillaumet, (1975) 43.
127_
tf_ Yasuda
128.
H.-J.
129.
R-B_
King
and J-C.
Cloyd,
Jr.,
J_ Am. Chem. Sot.,
97
(1975)
46.
130.
R-B.
Kin9
and J-C.
Cloyd,
Jr.,
J.
97 (1975)
53.
%tze,
and F. L.
Mordenti,
and H_ Tani, Chem
Gerson,
J.
and P.
Tetrahedron
Ber.,
108
(1975)
Am. Chem. Sec., Caubere.
Lett_,
J.
97
(1975)
Organomet.
(1975)
3556.
Chem.,
ll_
988.
clr,. Chm.
Sot.,
92
HEAVIER
ALKALI
ANNUAL
SURVEY
METALS COVERING
THE YEAR 1975
EDWIN M. KAISER Department 65201
of
Chemistry,
University
of
Missouri,
Columbia,
Columbia,
Missouri
(USA)
COilTENTS 1.
Physical
2.
Synthetic
Aspects
3.
Reactions
with
4.
References
PHYSICAL
1.
Organic
Chemical
Inorganic
the
of
with
lithium-formaldehyde
of
I [l]-
also
by differences
Kinetic sodium
have
Annual
These
do not
certain
which
results
with
ion-ketyls
bonding
led
Survey
the
authors
coverinq
to
the
not
pair
the
149
where
studies conclude
year
1975
in
of
contrkst
YO SCF
one minimum correto
those
two stablezspecies
explanations
ion-pairs.
by an -ab initio
presence
only
earlier
and solvation,
and conductometric
has been studied
suggest
are
ion
agree
sodium in
ion pair
results
to
scopy
145
Compounds
1
sponding
but
and Organometallic
ORGANIC CHEMICAL ASPECTS
UHF procedure,
exist.
133 113
The sodium-formaldehyde
the
Aspects
of
concerned
The discrepancies
obtained the
ion-pair
with
spectro-
are
reconciled
respectively.
on ethereal that
the
solutions carbanion
see J.Oryanome:al.Chm.,
of is
polystyryl-
a naked
one and
133(1375)1-38-
131
that the cation Na(DME)*+(II)
in dimethoxyethane
(DME) can be described
by the kinetic
entity
; s
[Z]-
II
papers described
Several
phosphino,
acidities
functional
groups
often
a rough guide
give
carbanion
as tentative,
[3]_
at best.”
the gas phase [4]. species
to carbanion derived
and other
earlier
establishment metric
cussed.
pKa values Indicators
measurements
are ascribe-1
delocalized.
Many earlier of certain available
nitriles
of acidities
kinetic
acidi ties
regarding
rela-
must be regarded
in DPlSO
charge
in these
of the above two papers
paper which describes
the
in DMSOusing a spectrophoto-
pKa’s have now been changed and
compounds as a function to cover
same
and ketones
to the negative
The results
assigned
and compared
those of the same compounds in
ones are summarized in a full
method [5].
different
and even approach
scale
conclusions
of several
thio,
by these
‘*_ _ .at though
stabilities,
The acidities
of an absolute
activated
that
from kinetic
Such results
being extensively
have been determined
conclude
of car-
sulfonyl-contafning
carbon-acids
The authors
have been found to parallel
of certain
molecules
of several
stabilities
work in the area of acidities
acidities
and phenyl-substituted
with the kinetic
tive
additional
Thus, equilibrium
bon acids.
of solvent
the pK range of 8.3
are dis-
to 30.6
in DMSOare
listed. Another group of workers has presented
experimental
of a large
number of anions
derived
from carbon,
DMSO[6]-
Both charge delocalization
and steric
said
to affect
i
the solvation
The trifluoromethylsulfonyl
oxygen,
solvation
enthalpies
and halogen
hindrance
acids
to solvation
in
are
energies. group has been found to lie
between the nitro
135
and benzoyl tion
groups
in its
ihe use of
[7]_
ability
this
and other
and cyclopropyl
isopropyl, an estimate
moieties
to be made of
and thus destabilized.
have also and other
a variety
of substituted
dithianes
unrelated
study,
that of
the kinetic
tritiated
stabilize
and acyclic
conjugative been studied
of
III
indicating
substantially
are strained it
is concluded
with carbanions.
using cesium salts
in cyclohexylamine
acidity
data which allow
systems,
effect
ioniza-
to methyl,
anions
compounds in !lMSO[S],
triphenylmethane
carbanions
quantitative
to which cyclopropyl
a large
of hydrocarbons
groups attached
has provided
Eoth in the cyclic
Equilibrium-acidities
rt-hydrogen atoms towards
functional
the extent
that the S02CF3 group exerts
variety
to activate
and a
and cesium salts
[9]_
Finally,
has been found
in an
to be greater
that alpha-trimethylsilyl
and
than
qroups
[IO]. (=5i)3C3H III
The bridgehead
hydrogen H3, shown in structure
IV, has been found to under-
go exchange
in deuterated
methanol using sodium methoxide
temperature
of 25” [ll].
In contrast,
conditions. authors side
to state
of bridged
enolates
results
ihese
Hl in IV fails
along with those on other
that enolate
stability
chain
low
to exchange under these ring
systems have led the
in such polycyclics
is enhanced at the
boat forms but not at their
in locked
at the remarkably
forms is diminished
bows.
The stability
of similar
considerably.
IV
In
contrast
to
the
corresponding
non-phenylated
systems
V and VI,
the
rl-
c
136 hydrogens of VII and VIII are exchanged with deuterium rate suggesting
that
delocalization The results
the phenyl groups
from C4 to the double are discussed
at virtually
the same
in VII cause the elimination
of charge
bond at C6,7 previously
in relation
to earlier
observed
described
carbonium
in V [12]. ion
chemistry.
The influence
viewed [13]_ tunneling distribution orientation latter
of
ionic
association
Other papers in this
in the elimination
reactions
are noteworthy
reactions
area have addressed
of five
reactions
VIII
in B-elimination
of certain
from E2 reactions of similar
P
VII
VI
V
(j-J’”
a”
0
0
Z-phenylethyl secondary
the question systems
alkyl
in that such eliminations
of hydrogen
[14].
tromides
of Z-butyl-N.N-disulfonimides
hris been re-
the olefin
[15-j, (IX)
afforded
and the [16].
only
The l-
butene.
‘Y RSOR I N\SOZR IX A new type of conversion reactions specifically
1.3-dehydrohalogenation
of species presumably eliminate
like
has been proposed
X to XI effected
proceed
by potassium
via ring-opened
potassium
chloride
intermediates
to afford
to account
r-butoxide
for
[17].
XII which stereo-
trans-products.
the The
__..-_
_r._..
_.
.
..-.
138 In conjugation
100 MHz [243. the authors is
with the NMRspectra
that the proportionality
conclude
of
cation,
phenyl tropyllum
constant
10 ppm/uni t charge
of
open to question. Conformational
mobility
annulene has been studied are interpreted bonds leading
zation
sequence
The cyclodecatrienyl
A full tion
at a higher
and by proton
scopy.
compound undergoes
Such topomeri-
field
abstraction indicates
directly
&positions
rather
than via a Interestingly,
of 5000-G. by reaction
of XX by potassium the presence
electrocyclization
of fenchone
and sodium pyrene
by CIDHP at 60-G [26].
paper appeared which discussed
at the five
toponers.
nine
temperatures
about the neighboring
anion XVIII has been prepared
of the homoenolization
occurs
at various
sodium anthracene,
as evidenced
The NMRspectrum of XVIII at -65” this
between
has been found to occur
such CIDW is not observed
species;
The spectra
chemically.
ttio alcohols
XIX with potassium
of cis,cis,cis,trans-[9]-
of the trans-bond
of sodium naphthalene.
disproportionation
salt
N+iR[25]-
to a dynamic equilibrium
Protonation or
by proton
in terms of rotation
is demonstrated
with water
in the potassium
triene
amide [27].
of a symmetricai
at -41°.
the results
(XXI) [28].
was demonstrated
of
of a detailed That deuterium
examinaexchange
by 13C and ‘H NMRspectro-
_ .
L
139
Other papers describing included
13C NMR of
the following:
LL’9], ‘ii RI!.? of
alky!malonates S-ketoesters
NMRexperiments
hydrocarbon
of
are treated
anion of a nydrocarbon
of
above technique
and the
39 K NMRand a7Rb
species
in the presence
electron
is a %nction
to investigate
to study electron
and its
parent
1361,
of such systems
transfer
exchanges.
peculiarities
transfer
of certain
which
It has
is a function
ihree
The processes
other
oapers
used the
in systems XXII where n = 3 and
between N-n-butylphthalimide
and to investigate
chains
between the aromatic
of n and temperature_
they were bimolecuiar
have been
by XXII (n = 3 to 20) [34].
the ESR spectra
intramolecuiar
4 1353.
phthalimide
inorganic
and
on one end and the corresponding
end as illustrated
in turn,
as if
[31].
Finally,
the dynamic flexibility
that the shape of
which,
5-diketones
as measured by ESR spectroscopy
to investigate
the freqilency
moieties
processes
on the other
been deter;?ined
[32]_
on certain
diethyl
of certain anion
compounds
[33]_
transfer
a radical
of several
the oxanonatetraenyi
have been effected
chosen as a tool
and related
the sodium salts
adduct of a carboxamide
of dibenzo-18-crown-6 Electron
of carbanions
the sodium enolates
the ‘l-l NMRof
[30],
‘H ?c?R 01 an alkoxide
contain
NMRspectra
electron
transfer
radical
anion
in XXII where Ar =
[37]. Ar_CCHZ-fiArL XXII
The following
benzyl c39.
[38],
toluene
radical
401, mesitylene
radical
anion
[41],
radical
have been prepared
species
2.3-naphthobarrelane
phosphinyl)ethylene radical
anions
silyl-aniline5 RcfcrrncBp. :19
radical
1433,
phane derivatives
radical
[44], [45.
radical anions anions
and radical
46, 473.
anion [40].
[38,
39, 403.
several
of certain anions
e-
recorded:
benzene radical
2.3-naphthobarrelene
anion [41], [42],
ESR spectra
and their
radical
anion
anion
and trans-1.2-fi(diphenylhindered
triptycene
of a variety
alkylbiphenyl and [2.2]-paracyclo-
of ring
substituted
140 Ultraviolet
spectroscopy
evidence
for
tions
potassium
of
only
attributed this
carbanion
carbanion
or
kinetics
of
with
lithium
the bleached
papers
a variety
in this
solvent
methoxide
or of
the effect
of
though solu-
exhibited
the spectra
that state
the excited persisting
by the relative
spectra
from solutions
potassium
state
tightness
of
fluoradenide
ion pairs.
THF and dioxane
longer
the authors
Second,
the hydrogen of
area
of
spectroscopy
of N-sodioamino-N-heteroaromatics
in the amino forms
the presence
Specifically,
[48].
UV
on the
effected
behaved
by
differently
in THF than in dioxane. of
the aggregates
in
media.
spectroscopy;
that
ions,
direct
from disodiotetraphenylethylene
It was found
were rationalized
Two other
XXIV [SO]_
free
the first
suggested the presence of contact
photoejection
[49]_
the respective
exist
bonded,
to obtain
in this
been used to study
in the two solvents,
First,
fluoradenide
18-crown-6
electron
These results
in methanol
tetramethylamnonium
has also
a 530-nm pulse
pairing
to hydrogen
in the presence of spectroscopy
ion
has been employed
conclude like
microwave
exchange
base
that
XXIII,
proceeds
not in the tautomeric
via
between a a-ally1
brief
mention.
have been studied
in the crystalline
spectroscopy
reaction
deserve
state,
such comoounds
imino forms as
has been employed propylene
in
to demonstrate
and deuterated
intermediate
by infrared
DHSO in
[Sl].
0) i;+ I
XXIII
Concerning continued of
mechanistic
to be studied.
sodium biphenylide
determining
studies, The current
on cis-stilbene
step was the conversion
anion [52].
-_
-.
the isomerization investigation
where it of the cis-
of ewas centered
was determined
to trans-stilbene around
the use
that
the rate-
to the trans-stilbene
radical
141 TWO
papers
more
aromatic
with
radical
were reacted
anions -
with E-hexyl
clude
that the irreversible
state
with little
The second various
paper studied
etherealsolvents
to that
differences
in shapes of potassium,
P-chloroquinoline
anions
are described
reactions
with E-hexyl
These authors
radical
suggest
plots
enolates
XXV provided
of iodobenzene
Fragmentation
con-
transistion [53].
carried
that the negative
out in charge
of fluorides
rela-
paper discusses
the
in both papers.
are subjected
with this
and related
products
the authors
have been found to react
the reactions
Another paper concerned
and anthracene
fluoride
The latter described
halides
on the halide”
in such reactions anion.
alkyl
an early
delocaliration
the Arrhenius
chemistry [56].
“involves
and charge
but not lithium
[55].
similar
among others,
transfer
is more localized
to afford
photostimulation
thiolate
similar
of the naphthalene
Several
describes
electron
of certain
sodiumnaphthalene
bromide and chloride;
[54]-
state
the reaction
In the first,
bond breaking
in the ttansistion tive
describing
appeared
with
to
SRNl mechanism
compounds with certain
of intermediate
radical
anions
and rationalized.
xxv The term ERCl has been applied chain elimination
process
XXVI with XXVII to afford
to a unimolecular
as illustrated styrene
radical
anion-radical
by the light-stimulated
derivative
XXVIII [57].
Several
reaction
of
other
examples are included.
e-02N-C6H4
NO2
XXYI An alternative
mechanism for
the acyloin
condensation
has been presented
112 which
does not involve
sists
of
a series
of
a-diketones discrete
steps
XXIX-XXX1 illustrate
Structures
0"'
Instead,
[SS].
differing
only
?R'
three
?R'-
R-C-0-$R
the pathway proposed
one from the other of
the suggested
con-
by one electron_
intermediates.
; ?- ?' R-C=CR
R-C-O-CR 0-
xxx
XXIX
Reduction
of XXXII with potassium
C&S]_
These results
rather
than phenylated systems_
I
has been shown to afford
are in marked contrast
0
cyclononyl
xxx1
to similar
XXX11
which previously
Possible
mechanisms are
of
ketone
proposed
varying
depending
presumably
arise
cerned with the formation that species
like
for
of
have been reacted base
XXXIV
to give
of substrates
via aryne
intermediates.
of benzofurans
like
with several
products
upon choice
XXXIV are intermediates
hZ1n
the current
reaction.
Ph
enolates
in the presence
products
of alkylated
xxx111
chlorobenzenes
yields
XXX111
have been shown to afford
xxx11
A variety
reductions
FPh *_ ‘H
-
dianion
like
XXXVII where it
in their
*Z)n
xxxv
XXXIV-XXXVII
and base [60]. A second
formation
dialkylaminoin
Most of
the
paper was con-
is demonstrated [61].
; :
143
1,4-Rearrangement alkali
metals,
protonation. than
ion
has been
XXXVIII,
prepared
realized
[62].
1,2-rearrangements
could
not
from
to afford
and NMR spectroscopy
related
Evidence
of
and
be garnered
the
XXXIX
This
corresponding
as evidenced
1.4-migration
increases
to demonstrate
in
the
the
much less
Li<
presence
and
by carbonation,
is
order
chloride
of
facile CS.
non-classical
XL.
e-Ph-C6H4C(Ph)2(CH2)3M
Ph2!
(CH2)3C6H4-@‘h
XXXVIII
XXXIX Ph XL
Other of
the
studies
Stevens
and axial
Favorskii
reaction <
2.
SYNTHETIC ASPECTS A warning
about
organornetallic
chloryl safer
References
route.
p_ l-l9
deserve
include
mention
a quantitative
sigmatropic of
of
CIDNP study
pathways
in
3-(I;-haloacyl)indoles
certain
another
has been
dichlorinated
explosion
published
benzocyclobutene.
fluoride.
that
the
[66],
the mechanism
in
latter
the
[6S].
Favorskii
The desired
[69].
potassium
perchloryl
of and
[68].
fluoride
The current
explosion
t-butoxide.
n-butyllithium,
3-fluorobenzocyclobutene
base-
[67],
methylketones
involving
latter
reactions
2-bronobenzo[6,7]bicyclo[3_2_l]-act-6-en-3-one
the
of
[63].
and forbidden
rearrangements
equatorial
a mixture
rearrangements
rearrangement
1641 , allowed catalyzed
of
and an
occurred
has been
with
and perprepared
by a
c--
-
._--
..
-.
--
- - -_
144 Another described
strong
[70]
internal
to
propargyl butoxide group
potassium
and employed
terminal
(XLI.
the
XLII.
The reactions
that
are
of
facile
[70.
G = 0,
KOH to afford
R [72]_
in
acetylenes
compounds or
base,
contrathermodynamic
713.
N,
5)
XLIII,
3-aminopropylamide.
In another
have
been
or
XLIV
postulated
to
isomerization
study,
reacted
proceed
a variety
with
depending
has been
via
of
potassium
upon the diallene
of
base
-bis-
tand
the
intermediates.
= --R
xQ
XX
XLIV XL111
Metalation addition XLVI
of
(37%)
is
oxide
by trimethylsilypotassium
has been
found
to afford
followed
a mixture
of
by
XLV (28%)
and
[733.
synthesis
illustrated
3-methyl-l-butene
ethylene
Several their
of
new,
stable
being by the
cyclobutadienes
proton
abstraction
conversion
of
XLVII
have
been described.
by strong to XLVIII,
bases
[74].
the
last
step
The process
of
--
145
Double dehydrobromination addition C7S] -
of
dimethylamine
The authors
of
XLIX
has been
suggest
that
by potassium
found
the
to give
reaction
t-butoxide
followed
6-dimethylaminofulvene
proceeds
via
m-benzyne
by (L)
LI.
XLIX
Cyclopropane zation
of
disilazane
and cyclobutanone
chlorocyanohydrins Similar
[76].
aminocyanoepoxides
like
[77].
of
The subject
(n
= 2 or
cyclizations LIII
ring
Other cyclizations
781.
LII
cyanohydrins
have
to afford size
in
3)
such
been prepared by cycli-
have effected
been
by sodiohexamethyl-
carried
pyrrolidines
like
cyclizations
out
on certain
LIV
(G = NH, 0 or
H2)
has been discussed [77.
described in 1975 include the preparation of epoxides
from B-hydroxyalkylselenonium salts
[79] and of naphthyridines from dinitriles
[801-
PR Cl (CH2),CHCN
/
0
G
CN
Ar
Ar
ii
LII
4
LIII
LIV
Alkylation convenient
and subsequent
synthesis
of
oxidation
chain-extented
of
LV has been
and a-branched
found
a-amino
to constitute acids ; several
a
146
_
examples are listed
[81]. ‘:
(RS)2~=~-c~-~02c2bi5
LV Cyclobutanones tuents
are readily
systems like described
containing cleaved
LVI or LVII,
by basic
hydroxide,
[82,
(1luY) to afford
and methyllithium
to give
v-substituted
reductive
The nucleophiles
group.
substi-
In conjunction
831.
the method represents
of a carbonyl
a lkoxide,
or 3,x-trinethylenedithio
reagents
respectively
spiroannelations,
geminal alkylation
u,u-dibromo
acids,
with earlier
alkylation used to date
esters,
or include
and ketones.
respectively.
-sJ/-\,
( 4’ Other studies
in this
area that deserve
of LVIII with non-enolizable rt-ketosulfones
(LIX)
carbonyl-containing nucleophile
versus
carbonyl
0
to afford
the generation
functional
to a vinyl
cyclopropanes tives,
[84],
aldehydes
halide
epoxides
mention
include
the condensation
enol ethers
by conjugate
and a discussion
from the reactions
of the formation acid
of a of deriva-
compounds, and base [86].
X
SO2R”
M’
-._.,G ----Nu LX
LVIII
covered
LX (G =
addition
of a-haloacrylic
R
Several
of hypothetical
of Darzens intermediates
group or cyanide) [85],
CONU
papers discussed
included
aliphatic
semidiones.
bicyclo[3_2_0]hep-2-ene-6.7-semidiones
Systems specifically [87],
cycloheptane-1.2-
..
-emidiones certain
[88],
alkenyl
carbocyclic
Finally,
and cycloalkyl
conjugated
%
substituted
unsaturated
the preparations
have been described
3_
.. __,. ._-_. ._ .._
1,2-semidiones
1,2-semidiones
of saphthalene
cesiun
[89],
and
[90].
and phenylpyridine
cesium
[91].
REACTIONSNITH INORGANICAND ORGAhOMETALLIC COMPOlJiIDS Eight examples of complexes
of alkali
retal
hydrides
potassium
eXalilDle.
similarly,
this
and metallic examole,
hydride
no reaction
and LX11 have been observed
with certain
hydride
cation
LX:
magnesium alkyls
and di-c-butylnagnesium
and diphenylmagnesiun
are important
in
was observed
determining
and aryls
afford
give
[92].
For
LX1 in benzene;
LX11 in ether.
which
in the case of
in reactions
complex
!ithium
60th sol-rent
is
hydride
formed;
for
and dimethyl-
magnesium in ether. !4Mg2R4ti
YMgR2H LX1
A revieir discussing published
[93].
LXII
certain
The synthesis
aspects and crystal
(CSHS)2Ee2C2SbH8> has been described polyhedral
expansion
chloride.
Metallocarborane
been
synthesized
transistion
been
[95].
including
atoms migrate
several
corresponding
novel
to adjacent
nickelaboranes
Tetraborane the
halides
[94]_
of
certain
titanium, close
has also
has been anion
deprotonated
[99]_
Some of
discussed
[97,
by potassium
The preparation
and vanadium have
Gth
their
rearrangements
vertices
of
[96].
by a
and ferrous
the mixed-metal
polyhedral
polyhedral been
zirconium,
carboranes of
has been
of a new ferracarborane,
The compound was prepared
Four isomers
thermal
chemistry
sodium cyclopentadienide
with
complexes of
structure
(CsV5)2CoNiCB7H8 have been prepared_
presented
metal
4.5C2B7H9
by treatment
metal
carborane,
of
of metallocarborane
sodium,
then
bimetallochemistry in
has
which
The synthesis
the of
983. hydride B5H8-,
or
ammonia
to afford
B6Hg-,
B5H12-,
B6H11-;
148
and B7H12 are above
also
species
treatment alkene
Mixed
_
of [rOO].
aluminium
with
their
novet
to certain
t complexes
has been
area
of
metal
of
LX111
the
metal
metal [tO7],
of
reviews
anions,
of metal
of
this
species
analog
carbonyl
and with
has been alkylated
and
Thus.
such species
aromatics L-1143,
[112],
and methyl
from
the by
an
fialcoholates to give
of
with
its
in
published the
discusses Grignard have alkali
C8K [lOB]_
syntheses
reagents
metai
base NMR
of
[105].
effected
by
amalgams
Sodium-amalgam
IV halides
proton
concerned
disodium
been
species
with
LXIV
reduction
which
[109].
[IOS].
has
Reaction
has given recorded
of
anion [llO].
(csH,)MO(cO),(~~~~,)~
LX111
of
of
several
been
use
anions
and Group
(csH,)M~(c0)2(c~~~3)~l
Reactions
have
review
carbonyls
alkyl
presence
Finally,
for
yields
cyclopentadienide
new isonitrite-containing
by a variety
the
high
borabenzene
their
pentacarbonyl[methoxy(phenyl)carbene]chromium(O) LXV;
in
reported
[lOZ].
Another
alloy
in
sodium
compounds [tO4]_
has afforded
been alkylated
with
and with
sodium-potassium
synthesized
[l Ol] _
presented
compounds
corresponding
been
hydride
[103].
preparations
the
sodium
reacted
carbonyl
been
have
derivatives
as a transition
Convenient
of
been
patterns
tetracarbonylferrate
with
have
reactivity
organometallic
treatment
with
n-cyclopentadiene
the
have
A new route
chloride
corresponding In
trialkytboranes
diatkylbromoboranes
(borinato)cobal of
NMR and “B spectra
described.
LXIV
metal have
carbonyl been
anions
interacted
fluoroolefins organometallics
[113]. [115].
the
have
been
subject
with
a-chloroenamines
1.2,3-tri-&butylcyclopropenium
of
several
[111].
papers.
fluorocation
149 Carbonyl
ferrate
ferrates
have
bony1
aldehydes [lli’],
[116],
and to
With
with
sandwich
[122].
with
uranium
11241
sandwich
Finally, to
it
nickel,
with
reduce
THF has
Primary
involving
benzene
Alvarino.
been
silicon
substituted
cyclized
niobium
[125]
have
papers
prepared
from
LXVI
has been
[128].
by bases
in
the
l,l’-
to afford
been
Dipentadienylzinc and zinc
from additions
LXVII
of
and LXVIII
Chem_.
[127].
[129,
mono- and have
been
1301.
R2pCH2CH2PR2’ LXVIII
and H-B.
Schlegel,
J_ Organomet-
chloride
various
LXVII
H_ Guerra.
sodium
complexed
derivatives
RPHCH2CH2PH2
Pedulli.
of
chlorotriisopropylgermane
vinylphosphorus
like
The ability
has been enhanced by complexing
pentadienylpotassium
to certain
cyclooctatetraene
disclosed_
[126].
synthesized
negatively
with
mention.
bonds
salts
Several
and tantalum
deserve
Base-catalyzed
LXVI
J-H_
ferrocenes
carbon-halogen
polyphosphines
F. Bernardi. 6. 105 (1975) 711.
certain
de-
dipotassio-1,3,5,7-tetraphenylcycloocta-
stable
(i-C3H7)3GeNH2
2.
of
and copper
phosphines
l_
stereospecific
[123].
disubstituted
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