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Organogermyl Organostannyl and Organoplumbyl Phosphines Arsines Stibines and Bismuthines.

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Organogermyl, Organostannyl, and Organoplumbyl Phosphines, Arsines, Stibines,
and Bismuthines
By H. SchumannI*I
The preparation, properties, and reactions of the compounds named in the title are described, with particular reference to the possible participation of (p+d)x components in the
bonding between the group IVB and the group VB elements.
1. Introduction
A problem that is still of great interest in the field of
covalent inorganic compounds is the nature of the
bonding between silicon and oxygen. It is not yet
generally accepted that the unexpected stability of this
bond is due to decisive contributions from (p-d),,
double-bond components. A deeper insight into the
nature of the bond should, however, be obtainable by
comparison of the physical and chemical properties of
such covalent silicon compounds with the properties
of similar covalent compounds of the silicon hornologs germanium, tin, and lead. The investigations
should concentrate on the one hand o n tin as one of
the bonding partners and on the other on the homologous elements of oxygen and nitrogen. We have already reviewed the most important organometallic
compounds containing bonds between germanium,
tin, or lead and sulfur, selenium, or tellurium [I]. Covalent compounds of the group IV elements mentioned
with phosphorus, arsenic, antimony, and bismuth are
reported in the present article. These compounds were
unknown until a few years ago.
tion were obtained from tetraphenylstannane and
phosphorus in a sealed tube above 22O0Cr8-1ol. Triphenylphosphine and alloy-like tin phosphides were
also formed.
Diphenyltin and triphenylphosphine are formed first
between 220 and 230"C, and combine to form the
addition complex diphenyltin-triphenylphosphine(la).
Though this complex cannot be isolated, its existence
can be demonstrated by the formation of the stable
oxidation products diphenyltin oxide and triphenylphosphine oxide [11J. When the temperature is raised,
the complex ( l a ) rearranges into the stable isomer triphenylstannyldiphenylphosphine (2a), which in turn
is dephenylated by excess phosphorus. At 230 to
250 "C, for example, cyclic trimeric diphenylstannylphenylphosphine is formed. Between 250 and 280 "C
and with an excess of phosphorus, low molecular
weight compounds of this type undergo cleavage of
further P-C and Sn-C bonds to form highly polymeric organostannyl phosphines; however, these can be
isolated only in the form of their oxidation products
(Table 1). Above 280 'C, all the Sn-C bonds are broken; the end products of the degradation of phosphorus by tetraphenylstannane are triphenylphosphine
and tin metal.
2. Organogermyl, Organostannyl, and
Organoplumbyl Phosphines
2.1. Synthesis
Only two phosphines with organometallic substituents
were known in 1962. These were triethylstannyldiphenylphosphine, which was prepared in 1959 by
Kuchen and Buchwaldr21, and tris(trimethylstanny1)phosphine, which was described in 1960 by Bruker
et al. 131.
In analogy with the reactions of sulfur, selenium, and
tellurium with tetraorganostannanes l4-71, organostannyl phosphines of various degrees of polymeriza[ * ] Doz. Dr. H. Schumann
Institut fur Anorganische Chemie der Universitit
87 Wurzburg, Rontgenring 11 (Germany)
[I] H . Schumann and M. Schmidt, Angew. Chem. 77,1049(1965);
Angew. Chem. internat. Edit. 4, 1007 (1965).
[21 W . Kuchen and H. Buchwald, Chem. Ber. 92, 227 (1959).
[3] A . B. Bruker,L. D . Balshova, and L. 2. Soborovskii, Doklady
Akad. Nauk SSSR 135, 843 (1960).
Angew. Chem. internaf. Edit.
Vol. 8 (I9691
1 No. I 2
Whereas this reaction is not suitable for the specific
synthesis of definite organometal phosphines, the reactions of organometal halides with phosphine or
[4] M . Schmidt, H . J . Dersin, and H . Schumann, Chem. Ber. 95,
1428 (1962).
151 M . Schmidt and H . Schumann, Chem. Ber. 96,462 (1963).
[6] M . Schmidt and H. Schumann, Chem. Ber. 96, 780 (1963).
[7] M. Schmidt and H . Schumann, Z . Naturforsch. 19b, 74 (1964).
[8] H . Schumann, H . Kopf, and M . Schmidt, Angew. Chem. 75,
672 (1963); Angew. Chem. internat. Edit. 2, 546 (1963).
191 H . Schumann, H . Kogf, and M . Schmidt, Chem. Ber. 97,1458
[lo] H. Schumann, H . KopA and M . Schmidt, Z . anorg. allg.
Chem. 331, 200 (1964).
[ll] H . Schumann, H . Kopf, and M . Schmidt, Z . Naturforsch.
19b, 168 (1964).
93 7
Table 1. Oxidation products isolated as secondary products of the reaction of Sn(C6H& with Px (between 250 and 280 “C) (R = C6H5).
Structural units of
Organotin phosphonate
or phosphate
When diorganometal dihalides are used, the reaction
with diorganophosphines yields monomeric compounds of the type (5) 112-141, and the reaction with
monoorganophosphines yields oligomers of the type
Cyclic trimers of this type can be
isolated in yields of up to 85% with suitable experimental conditions L201. On the other hand, bis(ch1orodiphenylgermy1)phenylphosphine ( 3 4 is formed almost quantitatively from diphenylgermanium dichloride and phenylphosphine. With dipotassium
phenylphosphide in monoglyme/ether, the two ring
systems (3b) and (3c) are formed in a ratio of 3 : 1:
monopotassium phenylphosphide leads almost exclusively to (3b). The same mixture of (3b) and (3c) is
also formed on reaction of (3a) with K 2 P C 6 H 5 or
K H P C 6 H s 1211.
2 R,GeCl,
+ RPH,
k1 61
organophosphines (in the presence of triethylamine
as a hydrogen halide acceptor) has been found to be
very specific. Owing to the instability of the products,
rigorous exclusion of moisture and oxygen is necessary.
Thus triorganogermanium, triorganotin, or triorganolead halides react with diorganophosphines to give
products of the type (2)112-16aI, while with monoorganophosphines [12,16-17aI
phosphine [12,16,
18,191 they form compounds such as
(3) and ( 4 ) .
2 R2GeC12
-2KC1, -2HCI
R,Ge, ,GeR2
The reactions of diorganometal dihalides with phosphine itself also give polymeric organometal phosphines, but in this case containing the structural units
R 2 M ( and ;P 1211.
In the special case of the reaction of diphenyltin dichloride with phosphine, small quantities of a benzenesoluble compound (6) were isolated as well as high
polymers; an adamantane skeleton has to be proposed
for this compound [211.
[12] H. Schumann, H . Kopf, and M . Schmidt, J. organometallic
Chem. 2, 159 (1964).
[13] F. Glockling and K . A . Hooron, Proc. chem. SOC. (London)
1963, 146.
[14] E . H. Brooks, F. Glockling, and K . A . Hooton, J. chem. SOC.
(London) 1965, 4283.
[15] H . Schumann, P. Schwabe, and M. Schmidt, J. organometallic Chem. I , 366 (1963/64).
[16] H . Schumann, P . Schwabe, and M . Schmidt, Inorg. nuclear
Chem. Letters 2, 309 (1966).
[16a] H . Schumann, P . Schwabe, and 0 . Stelzer, Chem. Ber. 102,
2900 (1969).
[17] H . Schumann and A . Roth, J. organometallic Chem. 11, 125
[17a] I . Schumann-Ruidisch and J . Kuhlmey, J. organometallic
Chem. 16, P 26 (1969).
[18] H . Schumann, A . Roth, 0 . Stelzer, and M . Schmidt, Inorg.
nuclear Chem. Letters 2, 311 (1968).
[19] I . Schumann and H. Elass, Z . Naturforsch. 21b, 1105 (1966).
[20] H . Schumann and H . Eendu, Angew. Chem. 80, 845 (1968);
Angew. Chem. internat:Edit. 7, 812 (1968).
[21] H . Schumann and H . Benda, unpublished.
Angew. Chem. internat. Edit.
/ Vol. 8
1 No. 12
Phenyltin trichloride reacts with diphenylphosphine
to form monomeric tris(dipheny1phosphino)phenylstannane (7) 1121 and with phenylphosphine to give a
phenylstannylphosphine (8) (yield 5 %) having the
composition (C6H$n)2(PC6H&,, together with high
polymers of unknown structure. The IR and 31P-NMR
spectra 1211 of (8) indicate a bipyramidal structure with
three phosphorus atoms in equatorial positions and
two tin atoms in axial positions.
Methyltin and butyltin trichlorides give only highly
polymeric reaction products with phosphine. On the
other hand, small quantities of a tetrameric phenylstannylphosphine (9) having a cubane structure can
be isolated from the polymer mixture obtained from
phenyltin trichloride and phosphine 1221. Finally, tin
tetrachloride reacts with diphenylphosphine to give
tetrakis(dipheny1phosphino)stannane (10) I 121.
2%P R
R,Sn-P ,Sn,
[22] H . Schumann and H . Benda, Angew. Chem. 80, 846 (1968);
Angew. Chem. internat. Edit. 7, 813 (1968).
[23] H . Schumann, H . Kopf, and M . Schmidt, Chem. Ber. 97,
3295 (1964).
[24] J . G. M . Campell, G. W. A . Fowles, and L. A . Nixon, J. chem.
SOC.(London) 1964, 1389.
[25] A . B. Bruker, L . D . Balashova, and L . 2. Soborovskii, Russ.
Pat. 170976 (1965); Chem. Abstr. 63, 9985c (1965).
[26] L . D . Balashova, A . B. Bruker, and L. Z . Soborovskii, 2. obSP.
Chim. 35, 2207 (1965).
[27] A . B. Bruker, L . D . Balashova, and L . 2. Soborovskii, Russ.
Pat. 170977 (1965); Chem. Abstr. 63, 9985d (1965).
Angew. Chem. internat. Edit.
1 Vol. 8 (1969)1 No.
P ,SnRz
not yet been fully clarified, with formation of polymeric
cyclic phenylstannylphosphines such as (11) and (12) [*31.
Reactions of this type have also allowed the preparation of a trigonal bipyramidal phenylgermylphosphine
of the type (8) and a heptameric phenylgermylphosphine (C&sGeP)7 from phenylgermaniurn tribromide
and KzP(C6Hs) or Na3P respectively[zll.
Organophosphines also react with organotin oxides 128,
291 and with organogermylamines [13,14, 17a719,30,31,
341 and organostannylamines 132,331 with liberation of
water or amine and formation of corresponding
metal phosphines.
Phosphines in which the phosphorus atoms carry different organometallic residues are also obtainable [16a 351. Thus bis(triphenylstanny1)phenylphosphine
is split by butyllithium in benzene solution with
formation of butyltriphenylstannane and lithium
phenyltriphenylstannylphosphide (13). This product,
which cannot be isolated, reacts with triphenylgermanium bromide and triphenyllead chloride to form the
compounds (14) or (15) with mixed substituents
Lithium bis(triphenylstannyl)phosphide, which is
obtained in the same way as (13) from tris(tripheny1stanny1)phosphine and butyllithium, reacts similarly.
In addition to this versatile method, other syntheses
for phosphines with organometallic constituents have
also been developed in recent years. Examples of such
syntheses are the reactions of organo-germanium or
organotin halides with alkali metal organophosphi& [2,3,8,12-14,17a, 19,21,23-251 and of triphenylstannyllithium and phenylchlorophosphines [8,2326271:
Care must however be taken in the last reaction to ensure that
the phosphorus chloride in question is present in excess right
t o the end of the reaction. Otherwise the initially formed
monomeric reaction products are attacked by the strongly
nucleophilic triphenylstannanide ion in a manner that has
(15a). M = Ge
(ISbi, M = Pb
X = C1, B r
[28] K . Isskib and B. Walther, J. organometallic Chem. 10, 177
[29] W. P . Neumann, 3. Schneider, and R . Sommer, Liebigs Ann.
Chem. 692, 1 (1966).
[30] J . Satgi and M . Baudet, C.R. hebd. Seances Acad. Sci., S e r.
C 263, 435 (1966).
1311 J . Satgd and C. Couret, C.R. hebd. Seances Acad. Sci.,Ser.
C 264, 2169 (1967).
[32] K . Jones and M . F. Lappert, Proc. chem. SOC.(London)
1964, 22.
[33] K . Jones and M . F. Lappert, 3. organometallic Chem. 3, 295
[34] I . Schumann-Ruidisch and J . Kuhlmey, unpublished.
[35] H . Schumann, P. Schwabe, and M . Schmidt, Inorg. nuclear
Chem. Letters 2, 313 (1966).
2.2. Physical Properties
Apart from the alkylgermyl and alkylstannyl derivatives which are liquid under normal conditions, all
the known phosphines of this type are colorless to light
yellow crystalline solids (Table 2). They dissolve
readily, and without decomposing, in aromatic
hydrocarbons and in some ethers, such as tetrahydrofuran. Aliphatic hydrocarbons such as pentane, or
Table 2. Organogermyl, organostannyl, and organoplumbyl phosphines.
M.p. ( "C)
B.p. ("C/torr)
11, 16al
126 (decomp.)
140- 142
127-1 30
[16, 16a1
[16a, 191
10 (decomp.)
125- 126/0.3
[24, 32, 331
~ 4 1
L8, 12, 16a,
150-1 51/0.3
136- 137/3
1IS- 118
110 (decomp.)
100 (decomp.)
110 (decomp.)
10 (decomp.)
110 (decomp.)
methylcyclohexane are excellently suited for recrystallization.
The thermal stability of these compounds varies considerably. Thus organogermyl and organostannyl phosphines generally decompose only above 200 "C in an
uncontrollable manner, whereas organoplumbyl phosphines decompose at very low temperatures with deposition of lead. Trimeric dimethylstannylphenylphosphine (16) is also thermally unstable, and decomposes above 130 "C to give bis(trimethylstanny1)phenylphosphine (17), cyclopenta(pheny1phosphane)
(18), and tin [2OJ.
+ Sn
[ ( C H ~ ) Z S ~ - P C+
~ H ~[ ~
~ H ~ ~ S ~ I ~ P C S (CsHsp)~
The vibration spectra of the organometal phosphines
mentioned (Table 3) should contain, in addition to
thevibrations of the methyl groups and the substituentdependent and substituent-independent vibrations of
the phenyl rings, a skeletal vibration vM-P for compounds of symmetry C, and three skeletal vibrations
vas M-P-M, vs M-P-M, and 8M-P-M for compounds of symmetry Czv as IR- and Raman-active
vibrations. Four-particle molecules of the type M 3 P
with a planar arrangement of the atoms, corresponding
to the symmetry D 3 h , should give four skeletal vibrations, i.e. one symmetrical and one antisymmetrical
stretching vibration, and two bands in the long-wave
region of predominantly deformation character. The
symmetrical stretching vibration is IR-inactive. With
a trigonal pyramidal arrangement (symmetry C,,),
the nature and number of the vibrations remain the
same, but the symmetrical stretching vibration is also
IR-active. The fact that all four skeletal vibrations d o
in fact occur both in the I R and in the Raman spectra
of the tris(triorganoe1ement)-substituted phosphines
thus clearly shows the pyramidal structure of these
molecules and indicates the absence of strong (p+d)K
multiple bond components [16a339-41].
The long-wave shifts of the frequencies v M-P, Vas and
vs M2P or M 3 P , and 8 M 2 P or 8 M 3 P on replacement
of M = Ge by Sn and Pb are due to the increase in the
mass of the triorganoelement groups in the same direction. The differences vas - vs (M-P-M) increase
from 24 cm-1 for [(C,jH&Ge]2PC6H5 to 41 cm-1 for
the analogous tin compound, and 35cm-1 for the
corresponding lead derivative. This indicates an increase in the angle at the phosphorus due to the increase in the bulk of the triphenylelement unit.
The chemical shifts of the singlets that are found in
every case as expected in the 3 1 P - N M R spectra
(Table 4) [40,411 have surprisingly high positive values,
which are exceeded only by the value for white phosphorus (8 = 462 =t2 ppm 1403). It is also found that the
8 values vary in the series [(C6H5)3Sn]3P,
[36] I. Schumann-Ruidisch, H. Blass, and J . Kuhlmey, unpublished.
[37] H . Schumann and U . Arbenz, unpublished.
[38] A. 8. Bruker, L . D . Balashova, and L. Z . Suboruvskii, Z.
obSE. Chim. 36, 75 (1966).
1391 R . E. Hester and K . Junes, Chem. Commun. 1966, 317.
[40] G . Engelhardt, P . Reich, and H . Schumann, 2. Naturforsch.
226, 352 (1967).
[41] H. Schumann, P. Schwabe, P . Reich, and G. Engelhardt,
Angew. Chem. internal. Edit. 1 Vol. 8 (1969)
/ No.
Table 3. I R and Raman frequencies of organogermyl, organostannyl, and organoplumbyl phosphines.
286 m
320(3) p
311 (1)
284(4) p
294(1) p
351 s
313 s
88 m
88 m
88 w
88 (2)
153 m
123 w
171 (1)
oxygen-free atmospheres. The oxidation, either on
simple exposure to air or (always quantitatively) with
hydrogen peroxide in ethanol, proceeds in accordance
with the general equation
0 2
with the formation of organometal phosphinates. The
possible intermediates phosphine oxide (20) or phosphinite (19) have never been isolated in this reaction.
[(C6H5)3SnhPC6H5, (C6H5)3SnP(C6H5)2, P(C6Hd3 in
a manner that indicates the absence of (p-fd), bond
components between phosphorus and tin. As expected, however, the variation of the 8 values in
such series of compounds is determined, not by one
variable, but by several parameters that act with or
against one another. The 31P-117-119Sn coupling
constants, which are absolutely essential for a conclusive discussion of the situation, are not yet known.
Pure po(P)-(sp3)o(Si) bonds are assumed for similar
organosilylphosphines on the basis of detailed
31P-NMR spectroscopic measurements 1421.
Even when C,N-diphenylnitrone, 1,2-dihydroisoquinoline N-oxide, or benzonitrile oxide is used as a
specific oxidizing agent, triphenylstannyldiphenylphosphine for example is entirely oxidized to the final
stage, i.e. to the phosphinate.
Attempted independent syntheses of one of the two intermediates of this oxidation in particular were unsuccessful in
the case of triphenylstannyl diphenylphosphinite ( 1 9 ~ 1which
is extremely sensitive to oxygen, whereas triphenylstannyldiphenylphosphine oxide (20a) escapes isolation by immediate
rearrangement into the isomeric phosphinite [431.
2.3. Chemical Properties and Reactions
2.3.1. O x i d a t i o n
The sensitivity of organogermyl, organostannyl, and
organoplumbyl phosphines toward oxygen 1431 depends mainly on the number and nature of the organic
residues used to block the unwanted valences of the
metal. Alkyl compounds are more sensitive than the
corresponding phenyl derivatives toward oxygen. The
attack of oxygen is slowest on tetrakis(dipheny1phosphino)stannane (10) and tris(triphenylstanny1)phosphine, whereas all the other organometal phosphine
derivatives investigated can be safely handled only in
[42] E . Fluck, H. Burger, and (1. Coefze, 2. Naturforsch. 22b,
912 (1967).
[43] H. Schumann, P . Jutzi, A . Roth, P. Schwabe, and E. Schauer,
J. organometallic Chem. 10, 71 (1967).
Angew. Chem. internat. Edit. 1 VoI. 8 (1969) J No. 12
Thus all the compounds described in the literature as organostannylphosphine oxides are in fact probably the corresponding phosphinates (21) as has already been stated by a number
of authors c44-491.
[44] B. A . Arbusov and N . P. Grechkin, J. gen. Chem.
(English transl. of z. obBE. Chim.) 17, 2166 (1947).
[45] B. A . Arbusov and N . P . Grechkin, J. gen. Chern.
(English transl. of 2. obBE. Chirn.) 20, 107 (1950).
[46] B. A . Arbusov and A . N . Pudovik, J. gen. Chem.
(English transl. of
obBC. Chim.) 17, 2158 (1947).
[47] H. Schindelbauer and D . Hammer, Mh. Chern.
94, 644
[48] Y. Nagae and K . Wakamori, Jap. Pat. 4515 (66) (March 25,
1963); Chem. Abstr. 65, 229811 (1966).
[49] B. A . Arbusov and N . P . Crechkin, Izvest. Akad. Nauk
SSSR, Otdel. chim. Nauk 1956,440.
94 1
These results and the fact that organotin phosphinites
(19) remove oxygen even from organostannanols to
form organotin phosphinates [28J suggest the following
oxidation course:
solutions. The structure of the phosphine can be
readily deduced from the degradation products
(Table 1).
The organometal phosphines first add one oxygen
atom to form the phosphine oxides. The strengthening
of the metal-phosphorus bond is lost with the blockage
of the originally free electron pair on the phosphorus.
This bond is accordingly broken, and the phosphine
oxide gives a phosphinite in a reverse Arbusov rearrangement. The subsequent addition of a second
oxygen atom to the now restored lone pair of the
electrons on the phosphorus leads to the formation of
phosphinates. Since the second oxygen is added more
2.3.3. P o l a r I n s e r t i o n R e a c t i o n s
rapidly than the first, only the phosphinates are obtained as stable end products in every case. Triphenylstannyldiphenylphosphine reacts similarly with elementary sulfur to give (Zlb), whereas bis(tripheny1-
The metal-phosphorus bond of organogermyl and
organostannyl phosphines can be broken by 1,2-dipolar reagents [50,51,311. For example carbon disulfide
is inserted between germanium and phosphorus in
triethylgermyldiethylphosphine and between tin and
phosphorus in triphenylstannyldiphenylphosphineto
form triethylgermyl diethylphosphinodithioformate
(22a) and triphenylstannyl diphenylphosphinodithioformate (22b) respectively.
COS, CIzCS, (NH&CS, C6H5NC0, and C6HsNCS
also react as 1,2-dipoles to give the compounds shown
in Table 5. Cleavage with COz, on the other hand, has
been observed only in analogous organosilyl phosphines [521.
Table 5. Reaction products from organogermyl and organostannyl phosphines with
1,2-dipolar reagents
Reaction product
M.P. ("C)
(decomp. pt.)
[a] B.p. 98
stanny1)phenylphosphine and tris(triphenylstanny1)phosphine give, not the expected thiophosphates but
only their decomposition products, i.e. bis(tripheny1stannyl) sulfide and polymeric phenylphosphorus sulfides or P2S5 [431.
2.3.2. H y d r ol y si s
Perphenylated organogermyl, organostannyl, and
organoplumbyl phosphines are not hydrolyzed in the
absence of air, probably because of insufficient wetting
by water [I]. In alkyl-substituted compounds the metalphosphorus bond is broken with formation of phosphines and germoxanes, stannanols, or plumbanols 111.
All known organometal-substituted phosphines are
decomposed in this way by alcoholic sodium hydroxide
[bl B.p. 83 "CjO.1torr.
[cl B.P. 92 Y70.2 tom.
In analogy with the insertions in Si-"53-563
Sn-N compounds L32,571, these reactions presumably
also proceed by a polar four-center mechanism
via (23).
[50] H . Schumann, P . Jutzi, and M . Schmidt, Angew. Chem. 77,
812 (1965); Angew. Chem. internat. Edit. 4, 787 (1965).
[51] H . Schumann and P. Jutzi, Chem. Ber. 101, 24 (1968).
1521 E. W. Abel and I. H . Sabherwal, J. chem. SOC.(London)
(A) 1968, 1105.
[53] H . Breederveld, Recueil. Trav. chim. Pays-Bas 79, 1126
(1960); 81, 216 (1962).
1541 G . Oertel, H. Malz, and H . Holtschmidt, Chem. Ber. 97, 891
(1 964).
[55] W. Fink, Chem. Ber. 97, 1424, 1433 (1964).
[56] W. W. Limburg and H . W. Post, Recueil. Trav. chim. PaysBas 81, 430 (1962).
[57] T . A . George, K . Jones, and M. F. Lnppert, J. chem. SOC.
(London) 1965, 2157.
Angew. Chem. internat. Edit. / Vol. 8 (1969)/ N o . 12
Sn[P(C6H&]4 also reacts, though very slowly, with
CS2 and phenyl isocyanate with cleavage of all four
tin-phosphorus bonds; f(C6H&Sn]3P, on the other
hand, does not undergo this cleavage. The difference
in the behavior of these two stannyl phosphines again
points to the participation of the lone pair of electrons
on the phosphorus in the tin-phosphorus bond.
Whereas there are four lone pairs of electrons available o n
the phosphorus atoms of Sn[P(C6H&]4 to strengthen the
bonds to a single tin atom, so that full use is not made of
them, the lone pair of the single phosphorus atom in
[ ( C ~ H ~ ) & I ]is~ completely
“exhausted” by participation in
three tin-phosphorus bonds. Thus the electrophilic attack by
1,2-dipolar reagents is successful in the first case but not in
the second.
This reaction principle does not extend to 1,3-dipolar
reagents. Thus, whereas organostannyl phosphines are
merely oxidized by nitrones and nitrile oxides (431 and
d o not react with nitrilimines and diazomethane,
organic azides such as phenyl azide break the bonds
between phosphorus and the group IVA elements
mentioned to form novel iminophosphoranes‘such as
(24) and (25) 1171.
up a further phenylimine residue to form the stable
end product. The fact that reactions of this type
proceed rapidly with mono-, slowly with bis-, and
immeasurably slowly with tris-organometal-substituted
phosphines again points to participation of the lone
pair of P electrons in the M-P bond.
2.3.4. A d d i t i o n t o O I e f i n i c D o u b l e B o n d s
Triphenylstannyldiphenylphosphine reacts with ally1
chloride and with styrene to form chloromethyltriphenylstannylethyldiphenylphosphine(28) and phenyltriphenylstannylethyldiphenylphosphine (29) respectively(591; the products in both cases are in two
isomeric forms, which have not been separated.
(28a, h ) , R = CICH2, m.p. 39 “C
(290, h i , R = C ~ H S , m.p. 59 “C
The reaction with phenylacetylene stops at the stage
of the phenyltriphenylstannylethylenediphenylphosphine (30) in the forms (a) and ( b ) , even when a large
excess of triphenylstannyldiphenylphosphineis present (591.
By analogy with hydrostannation [6OJ, this reaction
may be assumed to proceed by a free-radical mechanism. This is supported both by the considerable increase in the yield on addition of catalytic amounts of
azodiisobutyronitrile and by the simultaneous formation of different isomers. In the reaction of triethylgermyldiethylphosphine with phenylacetylene, two
cis and two trans isomers could be detected by
1H-NMR spectroscopy C311. Acrylonitrile adds triethylgermyldiethylphosphine (311
trimethylstannyldiphenylphosphine 1611 exclusively to the ole-
(24a), M
(2461, M
(25a), M
(25b), M
decomp. pt. 170°C
m.p. 173-178 “C
m.p. 160°C
decomp. pt. 40 “C
The reactions may be assumed to proceed by initial
formation of an iminophosphorane of the type (26),
which is unstable (with tert-butyl residues on the
phosphorus and a trimethylsilyl group on the nitrogen, N ,P-organometal-substituted iminophosphoranes
of this type have now been isolated I-589, and rearranges
into an aminophosphine of the type (27) which takes
(27) C6H5
1581 0. J . Scherer and G . Schieder, Angew. Chem. 80, 83 (1968);
Angew. Chem. internat. Edit. 7, 75 (1968).
Angew. Chem. internat. Edit.
Vol. 8 (1969) 1 No. 12
(30a, b), m.p. 45 “C
finic double bond, while vinylogous carbonyl compounds such as mesityl oxide, acrolein, or cinnamaldehyde insert their carbonyl function between the
tin and the phosphorus in a polar reaction with trimethylstannyldiphenylphosphine to give compounds
of the type (31), with no attack on the olefinic double
bond 1611.
[59] H Schumann, P. Jutzi, and M . Schmidt, Angew. Chem. 77,
912 (1965); Angew. Chem. internat. Edit. 4,869 (1965).
[60] W . P. Neumann, Liebigs Ann. Chem. 659, 17 (1962).
[61] H . Schumann and A. Yughmai, unpublished.
With M = Si and M' = Ge, Sn, or P b because of the high
tendency of (CH3)3SiCI to be formed, and with M = Ge or
Sn and M' = P b because of the fast thermal decomposition
of the [(CH3),Pb]3P present in equilibrium, this exchange
proceeds quantitatively in the direction of the upper arrow;
for M = Ge and M' = Sn and for M = Sn and M' = Ge, on
the other hand, all four possible reaction products can be
detected together.
(31a), m.p. 90-95" C
2.3.5. P h o s p h o n i u m S a l t F o r m a t i o n
Organogerrnyl, organostannyl, and organoplumbyl
phosphines, unlike organosilyl phosphines 1621, d o not
form stable phosphonium salts. Organogermyl phosphines 113,141, and organostannyl phosphines 1x21 react
with Lewis acids only at very low temperatures to give
addition products, which quantitatively decompose on
warming, with cleavage of the Ge-P or Sn-P bond.
2.3.6. S y n t h e s i s of O l i g o m e r i c
The reaction of organostannyl phosphines with phenylphosphorus or phenylarsenic chlorides leads to stable
products containing two, three, or four directly linked
phosphorus atoms and compounds in which a phosphorus atom is linked to one, two, or three arsenic
atoms [64J. Thus the reaction of tris(trimethylstanny1)
phosphine with diphenylphosphorus or diphenylarsenic chloride leads to elimination of trimethyltin
chloride and formation of tris(diphenylphosphin0)phosphine or tris(dipheny1arsino)phosphine:
chloride also fail to give stable tetrakis(trimethy1stanny1)phosphonium chloride 1631.
As has been shown by N M R spectroscopy, exchange merely
occurs with the trimethylstannyl groups o n the phosphorus
atom. A 1 : 1 mixture of tris(trimethylstanny1)phosphine and
trimethyltin chloride gives only one singlet signal for all the
trimethylstannyl protons in the 1H-NMR spectrum, even at
-6O"C, whereas the original doublet signal of the stannyl
phosphine is no longer found. Since cryoscopic molecular
weight determinations and I R spectra clearly show that the
two components are present together in such mixtures, the
1H-NMR spectrum must be interpreted as resulting from a
very rapid exchange of the (CH3)3Sn groups via an extremely
short-lived pentacoordinate state of the phosphorus.
Similarly, diphenylphosphorus and diphenylarsenic
chlorides react with bis(trimethylstanny1)phenylphosphine to give the compounds (32a) and (32b) respectively.
Compounds of this type, of which bis(dipheny1phosphin0)phenylphosphine 1651 and tris(dipheny1phosphino)arsine 1661 have also been obtained by other
routes, are colorless when pure, crystalline, and soluble in ether, cyclohexane, and aromatic hydrocarbons.
Their structure has been verified by IR, Raman, and
3 1 P - N M R spectra (Table 6). Their sensitivity to oxygen
Similar exchange reactions, though in some cases with formation of new end products, occur between tris(trimethylsily1)-,
tris(trimethylgermy1)-, tris(trimethylstanny1)-, or tris(trimethylp1umbyl)phosphine and trimethylchlorosilane, trimethylgermanium chloride, trimethyltin chloride, trimethyllead
Table 6.
M.p. ( "C)
120- 123
169- 172
70 (decomp.)
185- 190
115-1 17
chloride, trimethylstannyldimethylamine, and bis(trimethy1stannyl) sulfide.
[62] G . Fritz, Angew. Chem. 78, 80 (1966); Angew. Chem. internat. Edit. 5, 53 (1966).
H. Schumann and 0 . Stelzer, unpublished.
Oligomeric phenylphosphines and phenylarsines.
IR (cm-1)
Raman (cm-1)
8 (ppm)
vaSPP,486, vSPP3 427
vaSAsP3 357, vSASP,280
vasPAs3 311, vSPAs3274
vaSAsAss285. vsAsAs3 262
vasPP3 481, vsPP3 426
vSPAs, 294
+16.9; -1-27.0
vasAsPz 3 1 1 vsAsPz 293
vasPAsz 354, vsPAs2 282
v,,AsAsz 293, v,AsAsz 262
vPAs 353
vsAsP2 297
vasPAs2 320, vSPAsz 275
vPAs 375
1641 H . Schumnnn, A. Roth, and 0. Stelzer, Angew. Chem. 80,
240 (1968); Angew. Chem. internat. Edit. 7, 218 (1968).
[65] E. Wiberg, M. van Ghemen, and G . Miiller-Schiedmayer,
Angew. Chem. 75, 814 (1963); Angew. Chem. internat. Edit. 2,
646 (1963).
1661 T. A. George and M . F. Lappert, Chem. Commun. 1966,463.
Angew. Chem. internat.
Edit. / Vol. 8 (1969) 1 No. I2
The complexes are formed quantitatively as colorless
crystals, which unlike the starting phosphines, are
surprisingly stable to atmospheric oxygen but are
often thermally very unstable.
The considerable increase in the coupling constant
that is always found o n transition from
the free phosphines (C = 9.80 Hz, Si = 4.62 Hz,
Ge = 4.00 Hz,Sn = 1.95 Hz, Pb = 0 Hz) to the complexes (Table 7) confirms the increase in the s character
of P-El bonds on transition from the substantially p3hybridized P atom in the free phosphines to the sp3
state in the complexes. The slight shift of the vas PE13
decreases as the number of phenyl groups bound to the
central P atom increases. [(C&&P]3P
very rapidly into triphenylphosphine, tetraphenyldiphosphane, and ( C ~ H S P ) ~ .
2.3.7. T r a n s i t i o n M e t a l C o m p l e x e s
It can be concluded from the chemical and physical
properties already mentioned that the lone pair of
electrons on the phosphorus in organometal-substituted phosphines makes a certain contribution to the
Table 7.
Transition metal complexes with organometal-substituted phosphine Iigands.
Pt. (“C)
v C 0 (cm-1)
13.8 [a], 2.0 It
phosphorus-metal bond in the sense of a (p-fd),
interaction. The phosphines discussed should therefore exhibit little or no tendency to occur in transition
metal complexes as 0 donors.
By reaction of tetracarbonylnickel with tris(trimethy1silyl)-, tris(trimethylgerrny1)-, tris(trimethylstanny1)-,
and tris(trimethylplumby1)phosphinesand with tris(tertbuty1)phosphine in tetrahydrofuran a t room temperature, however, it is possible to synthesize nickel(0)
complexes such as (33), in which tertiary organometalsubstituted phosphines with tetracoordinate phosphorus are present for the first time as ligands together
with carbon monoxide [67,67a1.
2074, 1995
2070, 1996
2057, 1968
2049, 1960
2037, 1965
2049, 1976
2062, 2000
1993, 1927
2001, 1947
2024, 1965, 1742 (vNO)
2016, 1960, 1739 (vNO)
2008, 1938, 1718 (vNO)
2020, 1960, 1740 (vNO)
1964, 1948, 1732, (vNO) 1717 fvNO)
2020, 1946, 1908, 1873
2024, 1946, 1908, 1880
2032, 1957, 1923, 1887
1990, 1710 (vNO) 1760 (vNO)
1763 (vNO) 1740 (vNO)
2058, 1934, 1901
2057, 1934, 1904
2053, 1927, 1898
2049, 2004, 1972, 1942, 1919, 1890
2049, 1996, 1972, 1965, 1927, 1887
2050, 1991, 1982, 1930, 1923, 1900
2017, 1936, 1913, 1905
2045, 1953, 1916, 1890
2058, 2008, 1965, 1910, 1890
2033, 1968, 1968, 1925
2045, 1905, 1880
2032, 2001, 1954, 1890
1923, 1848
1923, 1852
1919, 1852
413, 389
392, 316
352, 345
40 1
band observed on comparison of the IR spectra of the
free phosphines and of the complexes show that the
element-phosphorus bonds are only slightly weakened
by the complex formation. The stability of the complexes to oxygen supports the hypotheses that on oxidation of organometal-substituted phosphines, the
attack of the oxygen takes place on the “lone” pair of
electrons on the phosphorus, which is blocked in the
complexes by coordination with nickel and is thus no
longer available for electrophilic attack.
These phosphines containing tris(trimethyle1ement)
groups also react with hexacarbonylchromium [67a,681,
1671 H . Schumann and 0 . Stelzer, Angew. Chem. 79, 692 (1967);
Angew. Chem. internat. Edit. 6, 701 (1967).
[67a] H . Schumann, 0 . Stelzer, and U.Niederreuther, J. organometallic Chem. 16, P 64 (1969).
[68] H . Schumann and 0 . Stelzer, Angew. Chem. 80, 318 (1968);
Angew. Chem. internat. Edit. 7, 300 (1968).
Angew. Chem. internat. Edit. 1 Vol. 8 (1969) J No. 12
hexacarbonylmolybdenum, and hexacarbonyltungsten [67a, 1033, tricarbonylnitrosylcobalt [67a7683, pentacarbonyliron or enneacarbonyldiiron [67a,691, and tricarbonylcyclopentadienylmanganeseI67a, 1031 on UV
irradiation, with displacement of carbon monoxide to
give transition metal complexes of the types (34)
to (37).
manium, organotin, and organolead halides, as well
as tin tetrachloride, react with sodium diphenylarsenide in liquid ammonia to form organometalsubstituted diphenylarsines in which one to four diphenylarsine residues are bonded to the element in
quest ion,
Another series of compounds, in which one to three
triphenylstannyl residues are bonded to arsenic, can be
prepared by the reaction of triphenylstannyllithium
with phenylarsenic chlorides or arsenic trichloride in
tetrahydrofuran 1751.
M = C r , Mo, W; E l = C, Si, Ge, Sn, P b
Complexes in which phosphines with organometal
groups are present as polydent ligands have also been
reported [709711.
3. Organogermyl-, Organostannyl-, and
The yields of organostannyl arsine are generally low,
since side reactions such as condensation and transmetalation cannot be eliminated despite adherence to
special experimental conditions. Organostannyl arsines
can on the other hand be obtained without by-products
by reaction of organotin halides with organoarsines or
AsH3 in benzene in the presence of triethylamine as a
hydrogen chloride acceptor 1761.
3.1. Synthesis
R, R'
The first organometallic compounds containing covalent bonds between arsenic and an element of group
IVB, apart from a mention in a patent1721, were obtained in 1964 by Jones and Lappert[32,331 and by
Schumann and Schmidt 1731.
CH3, C6H5; n
The analogous tris(triorganogermy1)- and tris(triorganoplumby1)-arsines can be synthesized in the
same way 1181 or by reaction of trimethylgermyldimethylamine with AsH3 [193.
( C ~ H ~ ) ~ S ~ [ A ~ ( C ~ HCS ~
) ZH] ~Z S
, ~[A~(C~H
Sn[AS(C6Hs)2]4 can also be prepared by reaction of
the corresponding tin halides with KAs(C6Hs)z in
Table 8.
A large number of organostannyl arsines and some
organogermyl and organoplumbyl arsines were
prepared slightly later by Campell, Fowles, and
Nixon 1741 and by Schumann et al. 175-771. Organoger[69] H . Schumann and 0. Stelzer, J. organometallic Chem. 13,
P 25 (1968).
[70] J . ENermann and K . H. Dorn, Z. Naturforsch. 23b, 420
(1 968).
[71] E. W. Abel, J . P . Crow, and S . M . Illingworth, Chem. Commun. 1968, 817.
[72] Standard Oil Development Co., Brit. Pat 445813 (1936).
[73] H . Schumann and M . Schmidt, Angew. Chem. 76, 344
(1964); Angew. Chem. internat. Edit. 3, 316 (1964).
[74] J . G. M . Campell, G. W. A . Fowles, and L . A . Nixon, J. chem.
SOC.(London) 1964, 3026.
[75] H. Schumann, Th. Ostermann, and M . Schmidt, Chem. Ber.
99, 2057 (1966).
[76] H . Schumann and A. Roth, Chem. Ber. 102, 3713 (1969).
[77] H. Schumann and M. Schmidt, Inorg. nuclear Chem. Letters
I , 1 (1965).
Organogermyl-, organostannyl-, and organoplumbylarsines.
M.p. ("C)
B.p. ("C/torr)
170- 172/760
150- 152/1
140- 143/0.15
90 (decomp.)
130- 133
115 (decomp.)
Angew. Chem. internat. Edit.
[76, 78, 1041
[32, 33, 761
[75, 761
173, 75, 761
[75, 761
Vol. 8 (1969)
No. 12
Table 10.
liquid ammonia 1761. Methylstannyl and methylarsine
derivatives of this type cannot be synthesized by this
method; they undergo dismutation with methyl shift
to give Sn[As(C6H5)2]4 and ( C H ~ ) ~ S ~ - A S ( Cor~ H ~ ) ~
Sn(CH3)4 and ( C H ~ ) ~ A S - A S ( C H ~The
) ~ . organogermyl-, organostannyl-, and organoplumbylarsines
known a t present are listed in Table 8.
I Ref.
M . p . ("C)
3.2. Physical Properties
The organogermyl-, organostannyl-, and organoplumbylarsines largely correspond to the homologous
phosphorus compounds in their physical properties.
Thus alkylgermyl- and alkylstannylarsines are colorless
liquids that can be distilled without decomposing
under reduced pressure, while the corresponding
phenyl compounds and the organoplumbylarsines are
colorless to light yellow solids. They dissolve readily
and without decomposition in organic solvents such
as tetrahydrofuran, diethyl ether, or aromatic hydrocarbons. Their thermal stability is generally higher
than that of their phosphorus analogs. The I R (Table9)
and the (so far only incompletely measured) Raman
spectra again indicate the pyramidal structure of the
compounds. Some of the IH-NMR spectra of some
organometal-substituted arsines have been recorded [19,76,78,1041, but no theoretical information has
been deduced from the results.
Table 9.
Organometal arsinates.
IR and Raman frequencies of organometal arsines.
IR (cm-1)
Y GeAs 267
vasAsGe3 275, vsAsGe3 256
va,AsSn3 233, vsAsSn3 21 1 [a1
vasAsSna 244, vsAsSn3 21 1
vasAsSn2 234, v,AsSnz 217
vasAsSn2 237, vsAsSnz 190
vasAsSnz 236, v,AsSnz 213
vAsSn 203 [761, 226 I1041
vAsSn 188
vAsSn 180
vAsSn 199
v,,SnAsz 261, vsSnAsz 228
vasSnAss 262, vsSnAs3 228
vdSnAs4 260, 228
vaSAsPb3 208, vSAsPb3 182
vaAsPb3 207, v,AsPbs 175
dasAsSn3 223, vsAsSnp 209 cm-1
180 (decomp.)
280 (decomp.)
Compounds of this type have been prepared independently from organotin halides and diphenylarsinic acid
in the presence of triethylamine as a proof of their
structure 174,751.
1, 2, 3
The products of the type (38), which are found to be
identical, are colorless crystals of which only the dimeric 1741 alkylstannyl derivatives dissolve in organic
solvents. Oxygen-free water does not attack organostannylarsines, as is shown by the synthesis of a compound of this type in water[1041. Hydrogen peroxide
breaks the Sn-As bond of methylstannylarsine derivatives [78a1, the nature of the cleavage product providing evidence of the constitution of the starting arsine.
Polar reagents such as methyl iodide split the Sn-As
bond more slowly than the Sn-P bond to form
organotin iodides and tetraorganoarsonium iodides C74,78aI.
Triphenylstannyldiphenylarsine and bis(tripheny1stanny1)phenylarsine react with phenyl azide to form
the new organotin-substituted aminoiminoarsines (39)
and (40) respectively 178bl.
Tris(triphenylstannyl)arsine, on the other hand, is not
attacked by phenyl azide even in boiling benzene.
3.3. Chemical Properties and Reactions
Arsines containing organometal groups are sensitive
to oxygen. They are oxidized in air at various rates to
give isolable metal arsinates of the type (38) [78al
(Table 10).
0 2
M = Ge, Sn, Pb
[78] E . W. Abel and D . B. Bra&, J. organornetaliic Chem. 11,
145 (1968).
[78a] H. Schumann and A . Roth, Chern. Ber. 102,3725 (1969).
Angew. Chem. internat. Edit. 1 Vol. 8 (1969) 1 No. 12
+ 3 N,
C6H5 C6H5 CBH5
(391, m.p. 160-162 "C;
m.p. 152-155 "C
[78bl H. Schumann and A . Roth, Chem. Ber. 102,3731 (1969).
The high formation tendency of trimethyltin chloride
allows the use of organostannylarsines for the synthesis of interesting oligomeric phenylarsines, in which
up to four arsenic atoms are linked to one another 1641
(Table 6). Thus tris(trimethylstanny1)arsine reacts with
diphenylphosphorus or diphenylarsenic chloride to
form tris(dipheny1phosphino)arsine or tris(dipheny1arsino)arsine.
and bis(dipheny1arsino)phenylarsine can be prepared
similarly from diphenylphosphorus or diphenylarsenic chloride and bis(trirnethylstanny1)phenylarsine. Diphenylphosphinodiphenylarsine(41) can be
synthesized from trimethylstannyldiphenylarsine and
diphenylphosphorus chloride.
offered by the reactions of organometal halides with
NaSb(C6H& 174,77,801, Li3Sb [81,821, or SbH3 [18J in
liquid ammonia or benzene, or the reaction of triphenylstannyllithium with (C&5)2SbCI, C ~ H S S ~ C I ~ ,
or SbC13 in tetrahydrofuran [73,*01.
The last of these reactions gives the desired compounds
only in unsatisfactory yields, since transrnetalation
and condensation occur at the same time.
Stibines of the type (R3M)3Sb (M = Si, Ge, Sn) are
obtained in a very elegant manner from triethylstibine and triethyl- or triphenylsilane, -germane, or
-stannane with elimination of ethane. Stibines of the
type (42) can also be obtained by displacement reactions [83-851.
3 R3MH+ (CzH&Sb
With diphenylantimony or diphenylbismuth chlorides
and with methylphosphorus or methylarsenic chloride
the separation of trimethyltin chloride has also been
observed, but the oligomeric phenylarsinostibines or
phenylarsionobisrnuthines and oligomeric methylphosphinoarsines or methylarsinoarsines could not be
isolated, presumably because of their low stability.
A number of recent investigations 171,791 show that
organometal-substituted arsines can be bonded to
transition metals as complex ligands.
4. Organogermyl-, Organostannyl-, and
4.1. Synthesis
Organogermyl-, organostannyl-, and organoplumbylstibines, as expected, are very similar to the analogous
arsenic compounds. Useful synthetic routes were again
[79] H. Schumann and 0. Sfeizer, unpublished
Si, Ge, Sn; R
+ (R3M)3Sb+ 3 C2H6
C ~ H SC6H5
Finally, trimethylstannyldibutylstibine is formed as a
by-product in the presumably free-radial hydrostannation of ethynyldibutylstibine with trimethylstannane [86J-
4.2. Physical and Chemical Properties
Organometal-substituted stibines (Table 11) are
colorless liquids or crystalline solids that dissolve
readily and in the monomeric state in aromatic hydrocarbons or tetrahydrofuran. They can be recrystallized
from aliphatic hydrocarbons in the absence of oxygen.
Oxygen-free water does not attack phenylstannylstibines, presumably because of their non-wettability.
On the other hand all these compounds are sensitive
to oxygen. As in the oxidation of the analogous phosphorus and arsenic compounds, two oxygen atoms
are initially taken up per metal-antimony bond, but
in this case the oxidation does not lead to definite
products C74,801, since antimony-carbon bonds are
evidently also oxidatively broken in this case. Small
quantities of AlBr3 catalyze the thermal decomposition
[80] H. Schumann, Th. ostermann, and M . Schmidt, J. organometallic Chem. 8, 105 (1967).
[81] E . Amberger and R . W. Salazar, Sci. Commun., 11. Int.
Sympos. on Organosilicon Chem., Prague, Rep. 31, (1965).
[82] E. Amberger and R . W. Salazar, J. organometallic Chem. 8,
111 (1967).
[83] H. M . J . C. Creemers, Dissertation, University of Utrecht
[84] N . S . Vyazankin, G. A . Razuvajev, 0 . A . Kruglaya, and
G . S . Semchikova, J. organometallic Chem. 6, 474 (1966).
(851 N. S. Vyazankin, G. A . Razuvajev, 0 . A . Kruglaya, and
G . S . Semchikova, Doklady Akad. Nauk SSSR 166, 99 (1966).
[861 A . N . Nesmeyanov, A . E . Borisov, and N . N . Novikova,
Doklady Akad. Nauk SSSR 172, 1329 (1967).
Angew. Chem. infernat. Edit. / VoI. 8 (1969) f No. 12
Table 1I .
Organogermyl-, organostannyl-, and organoplumbylstibines.
B.p. ("Citorr)
M.p. ( " C )
157- 161/1
168- 170/0.13
179- 180/0.15
3 (CH3)3GeCI +Na3Bi
174- 17711.5
1 15 (decomp
150 (decomp
of [(C2H&Sn]3Sb to form Sn(CzH5)4, Sn, and Sb.
The cleavage of organostannylstibines with methyl
iodide 1741, benzoyl peroxide 1841, and organohalides 1841
has also been investigated.
5. Organogermyl-, Organostannyl-, and
In contrast with the organometal compounds of phosphorus, arsenic, and antimony, which have now grown
considerably in number, the number of organogermanium-bismuth and organotin-bismuth compounds
(Table 12) is very small. No compounds containing
covalent lead-bismuth bonds are known as yet. Apart
Organogermyl- and organostannylbismuthines.
M.P. ("C)
160-170 (decomp.)
138-142 (decomp.)
-+[(CH3)3Ge]3Bi + 3 NaCl
In NH,
The compounds with M = G e or Sn, whose chemical
properties have not yet been extensively studied, decompose at about 100 "C into hexaorganodigermanes
or hexaorganodistannanes and bismuth. In the presence of catalytic amounts of AlC13, they decompose
at even lower temperatures into tetraethylgermane or
tetraethylstannane, germanium or tin, and bismuth.
All the substances are sensitive to oxygen.
120 (decomp
Table 12.
B.P. (oC/torr)
114-1 16/0.1
167- 16812.5
184, 85,871
[84, 85, 871
[73, 831
from a passing reference to the use of triethylstannyldiphenylbismuthine as an antioxidant in lubricants 1721,
Schumann and Schmidt 1731 were the first to report the
successful synthesis of small quantities of tris(tripheny1stannyl)bismuthine from triphenylstannyllithium and bismuth chloride in tetrahydrofuran. Creemers 1831 increased the yield to more than 75 % by reaction of triethylbismuthine with triphenylstannane.
Tris(triethylgermy1)bismuthine and tris(triethy1stanny1)bismuthine 184,85371, as well as the extremely
sensitive tris(trimethy1germyl)bisrnuthine 1881, have also
been synthesized.
[87] 0 . A . Kruglaya, N . S. Vyazankin, and G . A . Razuvajev,
2. obSE. Chim. 35, 394 (1965).
1881 I . Schumann-Ruidisch and H . Blass, Z. Naturforsch. 226,
1081 (1967).
Angew. Chem. internat. Edit. J Vol. 8 (1969) No. 12
6. Comparisons
The starting point for the consideration of bonding in
covalent compounds between elements of groups IVB
and VB was the comparison of silicon-nitrogen compounds [891 with analogous silicon-oxygen compounds.
In investigations of this nature, strong (p-fd),, doublebond components were discussed for both the Si-0
and the Si-N bonds. The evidence presented to support the hypothesis of such strengthening of the Si-N
bond was above all the planar structure of the trisilylamineL901, on which strong doubt has now been
cast 1911.
The possibility of (p-fd), bond strengthening has also
been investigated for the homologs of the siliconnitrogen compounds. Thus (p-fd),
components were postulated not only for organostannylamines C92-943 but also for trisilylphosphine,
for which a planar structure was thought to have been
found '951. Views on this point have also been reversed
since then [961. Other investigations 142,621 refute such
a hypothesis. Thus trimethylsilyldiethylphosphine
reacts with ethyl iodide to give a stable phosphonium
salt, which melts without decomposition at 122 "C 1971.
HI [971, (BH3)2, BF3, BC13, and BBr3 [981 also add as
Lewis acids to the lone pair of electrons on the
[89] Cf. also 0. Wannagat in H . J . Emelius and A . G . Sharp:
Advances in Inorganic Chemistry and Radiochemistry. Academic
Press, New York 1964; E . A . V . Ebsworth: Volatile Silicon Compounds. Pergamon Press, Oxford 1963.
[90] J . Goubeau and J . Jimenez-Barbera, Z. anorg. allg. Chem.
303, 217 (1960).
[91] Th. D . Goldfarb and B. N . Khare, J. chem. Physics 46, 3319
[92] M . R . Kula, J . Lorberth, and E. Ainberger, Chem. Ber. 97,
2087 (1964).
1931 J. Lorherth and M . R. Kula, Chem. Ber. 98, 520 (1965).
1941 E. W . Rnnduif and J . J . Zuckerman, J:Amer. chem. SOC.
90, 3167 (1968).
[95] G. Davidson, E. A . V. Ebsworth, G . M . Sheldrick, and L . A .
Woodward, Spectrochim. Acta 22, 67 (1966).
[96] B. Beagle?, A . G . Robiette, and G . M . Sheldrick, Chem.
Commun. 1967, 601.
[97] G . Fritz and C. Poppenburg, Naturwissenschaften 49, 449
[981 H . Noth and W . Schragle, Chem. Ber. 98, 352 (1965).
phosphorus in silylphosphines or monogermylphosphines [1053.
Similar contradictions can be found for organogermyl-,
organostannyl-, and organoplumbylphosphines. The
course of the oxidation and the unsuccessful attempts
a t specific syntheses of organostannylphosphine oxides
or organostannylphosphonium salts lead one to attribute the stability of the tin-phosphorus bond to a
necessary (p-dx contribution, since the Sn-P bond
is broken as soon as the lone pair of electrons on the
phosphorus is engaged. The 1,2-dipolar additions of
carbon disulfide and phenyl isocyanate also support
this hypothesis, since Sn[P(C6H&]4 is accessible to
these reactions, whereas no electrophilic attack of
these 1,Zdipoles on [(C6H&Sn]3P is observed.
This interpretation of the covalent bond appears to be
opposed by the vibration spectra, which can be interpreted only in terms of a pyramidal structure of the
compounds, though it should be pointed out that it is
by no means certain that (p+d), double-bond components must be associated with a planar structure of
[99] E . A . V. Ebsworth, Chem. Commun. 1966, 530.
[lo01 E . W. Randall and J . J . Zuckerman, G e m . Commun.
1966, 132.
[loll H . Schumann, I. Schumann-Ruidisch, and M. Schmidt in
A . Sawyer: Organotin Chemistry. M. Dekker, New York, in
[I021 H. Schumann, 0. Stelzer, and H . Rosch, J. organometallic
Chem., in press.
[lo31 H. Schumann and 0. Stelzer, unpubtished.
[lo41 E . W. Abel, R . Honigschmidt-Grosich, and S . M . Illingworth,
SOC. (London), A 1968, 2623.
I1051 J . E . Drake and C . Riddle, J. chem. SOC.(London) A
1968, 1675.
the molecule [99,1001. The reactions of the tris(trimethylmetal)-substituted phosphines with carbonyl
compounds of the transition metals also show very
clearly that it is possible to use the lone pair of electrons on the phosphorus for coordinate bonding
without breaking the original P--MIV bonds.
As regards the stability of compounds of elements of
groups IVB and VB, the investigations carried out so
far show clearly that the most stable molecules are obtained with approximately equal covalent radii of the
bonding partners [84,8537,1011.
In the light of our present knowledge, the hypothesis
of the participation of the lone pair of electrons of
phosphorus, arsenic, antimony, and bismuth in the
bond with silicon, germanium, tin, or lead seems quite
feasible. The final decision should be left to detailed
physicochemical studies and structure analyses.
The author is grateful to Dip1.-Chem. Ulrike Arbenz,
Dr. H . Benda, Dr. P. Jutzi, Dr. H . KOpA U.Niederreuther, Fraulein Thea Ostermann, Dr. A . Roth, L. Rosch,
Fraulein Elke Schauer, Dr. P. Schwabe, Dr. 0. Stelzer,
and DipLChem. A . Yaghmai for their assistance in
his own work in this field. Thanks are also due to Prof.
Dr. M. Schmidt for valuable discussions, to Badische
Anilin- urrd Soda-Fabrik, Farbenfabriken Bayer, Farbwerke Hoechst, Werk Gendorf, and the Union Mini2i-e
du Haut Katanga for the free supply of valuable starting
materials, and to the Fonds der Chemischen Industrie
and the Deutsche Forschungsgemeinschaft for financial
Received: December 18, 1968
[A 732 IE]
German version: Angew. Chem. 81, 970 (1969)
Translated by Express Translation Service, London
Crystal Structure Analysis by Neutron Diffraction IF**]
By G. Will[*]
This second part of the article “Crystal Structure Analysis by Neutron Diffraction” deals
with the diffraction of neutrons by magnetically ordered crystals. Neutron diffraction is at
present the only reliable method for the determination of the magnitude, direction, and
spatial distribution of magnetic moments in crystalline substances. Since the magnetic
moments are essentially due to the unpaired electrons, the distribution of these electrons
in the crystal can be measured in this way.
1. Introduction
An important application of neutron diffraction is the
determination of magnetic spin structures in crystals
in the magnetically ordered state. The neutron, or
[*I Priv.-Doz. Dr. G. Will
Abteilung fur Kristallstrukturlehre und Neutronenbeugung
Mineralogisch-PetrologischesInstitut und Museum
der Universitat
53 Bonn, Poppelsdorfer Schloss (Germany)
[**I Part 11: Neutron Diffraction and Magnetic Structures. Part I: Neutron Diffraction at Atomic Nuclei 111.
rather its magnetic moment, acts as a probe, by means
of which the spatial electron spin distribution in the
crystal can be measured in atomic dimensions. Neutron
diffraction is at present the only method that allows
the reliable determination of the magnetic environmental relations between the individual atoms or ions
and of the long-range order of the spin. The investigation of magnetism and the use of constantly improving
magnetic materials has now become so important
that the chemist engaged in the preparation and
analysis of such compounds must also be familiar with
the magnetic properties and their investigation.
Angew. Chem. internat. Edit.
/ Yof. 8 (1969)/ No. 12
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organogermyl, organoplumbyl, bismuthines, stibines, arsine, phosphine, organostannyl
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