The synthesis by decarboxylation reactions and crystal structures of 1,n-bis(diphenylphosphino)alkane(pentafluorophenyl)-platinum(II) complexes

Article abstract of DOI:10.1002/zaac.200400465

Decarboxylation reactions between the complexes cis-[PtCl₂L] (L = 1,n-bis(diphenylphosphino)-ethane (n = 2, dppe), -propane (n = 3, dppp) or -butane (n = 4, dppb)) and thallium(I) pentafluorobenzoate in pyridine give cis-[PtCl(C₆F₅)L] and cis-[Pt(C₆F ₅)₂L] complexes in high yields with short reaction times. X-ray crystal structures of cis-[PtCl(C₆F₅)(dppe)] ·0.5 C₅H₅N, cis-[PtCl(C₆F ₅)(dppp)], cis-[PtCl(C₆F₅)(dppb)]·C ₃H₆O. cis-[Pt(C₆F₅)₂L] (L = dppe, dppp and dppb) and the reactants cis-[PtCl₂(dppp)] (as a CH₂Cl₂ solvate) and cis-[PtCl₂(dppb)] show monomeric structures with chelating diphosphine ligands in all cases rather than dimers with bridging diphosphines. ³¹P NMR data are consistent with these structures in solution.

Full text of DOI:10.1002/zaac.200400465

Artikel
The Synthesis by Decarboxylation Reactions and Crystal Structures of
1,n؊Bis(diphenylphosphino)alkane(pentafluorophenyl)-platinum(II) Complexes
Glen B. Deacon*,a, Philip W. Elliotta, Anja P. Ervena,b and Gerd Meyerb
a Monash/Victoria/Australia, School of Chemistry, Monash University
b Köln, Institut für Anorganische Chemie der Universität
Received November 1st, 2004.
Abstract. Decarboxylation reactions between the complexes
cisϪ[PtCl2L] (L ϭ 1,nϪbis(diphenylphosphino)Ϫethane (n ϭ 2,
dppe), Ϫpropane (n ϭ 3, dppp) or Ϫbutane (n ϭ 4, dppb)) and
thallium(I) pentafluorobenzoate in pyridine give cisϪ[PtCl(C6F5)L]
and cisϪ[Pt(C6F5)2L] complexes in high yields with short reaction
times. XϪray crystal structures of cisϪ[PtCl(C6F5)(dppe)] · 0.5
C5H5N, cisϪ[PtCl(C6F5)(dppp)], cisϪ[PtCl(C6F5)(dppb)] · C3H6O,
cisϪ[Pt(C6F5)2L] (L ϭ dppe, dppp and dppb) and the reactants
cisϪ[PtCl2(dppp)] (as a CH2Cl2 solvate) and cisϪ[PtCl2(dppb)]
show monomeric structures with chelating diphosphine ligands in
all cases rather than dimers with bridging diphosphines. 31P NMR
data are consistent with these structures in solution.
Keywords: Platinum; Diphosphine; Chelates; Decarboxylation;
Pentafluorophenyl; Crystal structures
Introduction
is chelating with a seven membered ring or whether bridg-
ing to give a dimer is preferred. Chelating has been pro-
posed for [PtCl2L] (L ϭ dppe, dppp, dppb) in both solid
state and solution on the basis of NMR measurements [12]
and is supported by XϪray crystallography for L ϭ dppe
[13] or dppp [14], but not for L ϭ dppb, and the structure
of cisϪ[PtCl2(dppb)] is now reported.
Decarboxylation reactions of metal carboxylates can pro-
vide useful syntheses of organometallic compounds [1Ϫ5].
Thermally induced reactions are effective for molecules
with electron withdrawing substituents in the organic
group, particularly polyfluorphenyl compounds [1, 4, 5],
where the method is competitive with Grignard and organ-
olithium routes and simpler to carry out. Radical induced
decarboxylation has enjoyed considerable success in the
synthesis of organomercurials [1Ϫ4], and has limited exten-
sions to cobalt [6] and platinum [7]. Thermal decar-
boxylation has mainly been used to give main group or-
ganometallics [1Ϫ4, 8], but some transition metal com-
pounds can be accessed [1Ϫ5], the most recent application
being to iridium compounds [9]. The method should be par-
ticularly suited to organoplatinum compounds, which are
relatively robust, but so far it has been used only to give
polyfluoroaryls with heterocyclic nitrogen donors [10] and
a number of hemidecarboxylated tetrafluorophthalates [11]
(see [7] for hydrocarbon analogues via radical decarbox-
ylation).
Results and Discussion
Syntheses
Both cisϪ[PtCl(C6F5)L] (1Ϫ3) and cisϪ[Pt(C6F5)2L] (4Ϫ6)
(L ϭ dppe (1, 4), dppp (2, 5), dppb (3, 6)) complexes can
be prepared in high yields with short reaction times by de-
carboxylation (eq. (1) and (2)), if platinum to thallium ra-
tios of 1:1 and 1:3.0Ϫ3.5 respectively are employed (Table
1). An attempted synthesis of cisϪ[Pt(C6F5)2(dppp)] (5)
using a 1:2 ratio gave a mixture of this compound (major
product) and cisϪ[PtCl(C6F5)(dppp)] (2). Whilst they can
be readily separated by chromatography (column or TLC),
this step is avoidable with appropriate stoichiometric con-
trol. In general shorter reaction times can be used for
cisϪ[PtCl(C6F5)L] than cisϪ[Pt(C6F5)2L]. Some of the for-
mer have been obtained at temperatures below reflux, one
even at room temperature, but use of boiling pyridine is
needed to give cisϪ[Pt(C6F5)2L] in high yields. Given that
TlO2CC6F5 is readily prepared in bulk amounts and can be
stored indefinitely [15], the short reaction time and simple
procedure make decarboxylation a far more convenient pre-
parative method for these complexes than the correspond-
ing synthesis from C6F5Li (or from the Grignard reagent),
which has been used to give 4 [16] and 1 [17].
We now present syntheses of monoϪ and bispentafluor-
phenylplatinum(II) complexes with 1,nϪbis(diphenyl-
phosphino)alkanes (n ϭ 2 (dppe), 3 (dppp) and 4 (dppb))
by decarboxylation, together with crystal structures of the
products. This establishes the generality of the method for
pentafluorophenylplatinum(II) complexes with chelating di-
phosphines. With the largest chain phosphine
Ph2P(CH2)4PPh2, it is of interest as to whether the ligand
* Prof. Glen B. Deacon
School of Chemistry
Monash University, VIC 3800, Australia
Tel: ϩ61 3 99054568
Fax: ϩ61 3 99054597
email: glen.deacon@sci.monash.edu.au
Z. Anorg. Allg. Chem. 2005, 631, 843Ϫ850
DOI: 10.1002/zaac.200400465
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
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G. B. Deacon, P. W. Elliott, A. P. Erven, G. Meyer
Table 1 Syntheses of organodiphosphineplatinum(II) complexes by decarboxylation
Platinum complex
n [mmol]
n(TlO2CC6F5)
[mmol]
t [min]
Organoplatinum(II) Products
Yield %
CO2 %
cisϪ[PtCl2(dppe)]
cisϪ[PtCl2(dppe)]
cisϪ[PtCl2(dppe)]
cisϪ[PtCl2(dppe)]
cisϪ[PtCl2(dppp)]
cisϪ[PtCl2(dppp)]
cisϪ[PtCl2(dppp)]
0.55
0.43
0.45
0.55
0.50
0.73
0.50
0.55
0.43
0.45
1.70
0.50
0.73
1.00
10
cisϪ[PtCl(C6F5)(dppe)]
cisϪ[PtCl(C6F5)(dppe)]
cisϪ[PtCl(C6F5)(dppe)]
cisϪ[Pt(C6F5)2(dppe)]
cisϪ[PtCl(C6F5)(dppp)]
cisϪ[PtCl(C6F5)(dppp)]a)
cisϪ[Pt(C6F5)2(dppp)] /
cisϪ[PtCl(C6F5)(dppp)]b)
cisϪ[Pt(C6F5)2(dppp)]
cisϪ[Pt(C6F5)2(dppp)]
cisϪ[PtCl(C6F5)(dppb)]
cisϪ[Pt(C6F5)2(dppb)]
72
75
94
83(90)
82
97
71/ 17
100
Ϫ
98
96(90)
99
99
ON RT
4 h 60 °C
10(30)
15
120
15
100
cisϪ[PtCl2(dppp)]
cisϪ[PtCl2(dppp)]
cisϪ[PtCl2(dppb)]
cisϪ[PtCl2(dppb)]
0.59
0.91
0.79
0.55
1.83
3.18
0.79
1.70
120
120
60
99
99
87
83
86
100
93
30
92
a) At 80 °C. Similar yield at boiling point.
b) Separated by preparative TLC.
cisϪ[Pt(C6F5)2L] and one similar to cisϪ[PtCl2L]. The 19F
NMR chemical shifts of each class are little affected by
change in diphosphine ring size with the chloride ligands at
slightly lower frequencies. Larger 3J(Pt,F) coupling con-
stants are observed for 4Ϫ6 than 1Ϫ3, consistent with
cisϪC6F5 groups in each and opposite to the trend for com-
pounds with transϪC6F5 groups [18]. There is a marginal
3
increase in J(PtF) for cisϪ[PtCl(C6F5)L] species with in-
creasing ring size, but for the cisϪ[Pt(C6F5)2L] complexes
the largest coupling is observed for 5. For the 31P NMR
spectra, the chemical shifts are closely similar to those of
the corresponding cisϪ[PtCl2L] complexes, except for 3
where the two resonances are separated by 21 ppm, but the
average corresponds to the chemical shift of the dichloro
complex. As cis stereochemistry in both solid state and
solution has been established by NMR spectroscopy for
cisϪ[PtCl2L] [12], supported by our determination of the
missing XϪray structure of 8 (Tables 2 and 3), cis mono-
meric structures for 1Ϫ6 in solution are clearly indicated.
1
For P trans to Cl of cisϪ[PtCl(C6F5)L], the J(Pt,P) coup-
ling constants are similar to those of cisϪ[PtCl2L] [12]
though the values are somewhat larger for the monochlor-
ides with the difference increasing (ca. 100, 200, 300 Hz)
with increasing ring size. Likewise, the values for P trans to
C6F5 are in general agreement with P trans to an aryl car-
bon atom including fluorocarbon groups [7, 11, 17] with
larger values for 4Ϫ6 than 1Ϫ3, paralleling the behaviour
Characterization
3
of J(Pt,F). Again the difference increases with increasing
All complexes were obtained microanalytically pure, 3 be-
ing obtained as an acetone solvate (confirmed by IR, NMR
and XϪray crystallography, below). The acquisition of
C6F5 ligands was evident from IR absorption bands at ca.
1500 (ν(CC)), 1060Ϫ1055 and 960Ϫ955 cmϪ1 (ν(CF)) for
all compounds. Whilst the cisϪ[PtCl(C6F5)L] complexes ex-
hibit a single band at 785 cmϪ1 attributable to a mode in-
volving platinumϪcarbon stretching [18, 19], two bands at
795Ϫ775 cmϪ1 for each of the cisϪ[Pt(C6F5)2L] complexes
ring size (ca. 50, 100, 200 Hz). On the other hand for both
1
groups of complexes the smallest J(Pt,P) value in any se-
quence is observed with the dppp complexes 2 and 5.
Electron impact mass spectra of representative complexes
show monomer parent ions and appropriate derived ions,
but the intensities of the former are low presumably due to
poor volatility. Electrospray mass spectra give high intensity
[M(monomer)ϩNa]ϩ and/or [M(monomer)ϩX]Ϫ (X ϭ Cl,
O2CH, CO2CCF3, etc.) peaks, but are complicated by sig-
nificant cluster ions ([2MϩNa]ϩ, [2MϩCl]Ϫ). These decline
in intensity on dilution and presumably arise through ClϪ
1
is indicative of cis-C6F5 ligands. In the H NMR spectra,
the ortho hydrogen atoms of cisϪ[PtCl(C6F5)L] complexes
are split into two groups, one similar to values for
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Z. Anorg. Allg. Chem. 2005, 631, 843Ϫ850

1,nϪBis(diphenylphosphino)alkane(pentafluorophenyl)-platinum(II) Complexes
Fig. 2 Molecular structure of cis-[Pt(C6F5)2(dppb)] (6); symmetry
related atoms (x, 0.5Ϫy, z) indicated by *.
Fig. 1 Molecular structure of cis-[PtCl(C6F5)(dppb)] (3), showing
disorder of C2A/B of the bridging carbon chain, hydrogen atoms
for the bridge have not been shown for simplicity.
or Naϩ linking two monomers. It is unlikely that diphos-
phine bridged dimers are present at the very high dilution
of ESMS measurements, given the strong evidence from 31
P
NMR spectra above for cisϪmonomeric complexes as
single species at much higher concentrations.
X؊ray crystal structures
X-ray crystal structures have been determined for 1Ϫ6 as
well as cis-[PtCl2(dppp)] · CH2Cl2 (7) and cis-[PtCl2(dppb)]
(8). Single crystals of 1 and 3 were obtained as solvates, 1
0.5 pyridine and 3 C3H6O, although the bulk sample of 1
was obtained pyridine free. Representative structures 3, 5
and 6 are shown in Figures 1Ϫ3, selected bond distances
and angles for 1Ϫ6 are listed in Table 2 and corresponding
data for cisϪ[PtCl2L] have been deposited.
Fig. 3 Molecular structure of cis-[Pt(C6F5)2(dppp)] (5).
In the solid state, all complexes are monomeric with chel-
ating diphosphines and cis anionic ligands. Specifically,
dppb, which is the most likely ligand to bridge, gives seven
membered chelate rings in all three complexes 3, 6 and 8.
In the light of these results, it is likely that
[Pt(C6Cl5)2(dppb)], which has not been structurally charac-
terized [20], has a similar arrangement. There is some devi-
ation from square planar stereochemistry, most notably
seen in the increase in the P1ϪPtϪP2 bite angle with in-
creasing ring size, and this is compensated by a sterically
disfavoured decrease in C51ϪPtϪC61 angles for 4Ϫ6 and
in P2ϪPtϪCl angles for 1Ϫ3. Analogous effects are seen
between the dichlorides 7 and 8. There is little displacement
(0Ϫ10.9(3) pm) of donor atoms and platinum from the best
fit plane of the five atoms, the deviation being greatest with
L ϭ dppp complexes (2 and 5). All corresponding
PtϪdonor atom bond distances of 1Ϫ3 are similar to each
other and to those of cisϪ[PtCl(C6F5)(dppm)] (dppm ϭ
Ph2PCH2PPh2) [21], hence they are unaffected by changes
in ring size from n ϭ 1Ϫ4 and even differences in solvation.
In the case of the dichlorides, one PtϪP distance increases
slightly (outside the 3 esd limit) from a six membered (7) to
a seven membered ring (8). The PtϪCl and PtϪP1 (trans
to Cl) distances are not affected by replacement of one Cl
by C6F5. However the PtϪP2 (trans to C6F5) distances of
1Ϫ3 are longer (6Ϫ8 pm) then those trans to Cl, well out-
side error limits, consistent with known trans influences
[22]. With 4Ϫ6, there are slight PtϪ(P,C) bond length in-
creases from L ϭ dppe (4) to L ϭ dppp (5), corresponding
with the largest increase in bite angle, perhaps arising from
greater crowding, though the comparison is made less clear
by there being two crystallographically different molecules
of 4 in the unit cell. Surprisingly, the change from a sixϪ
to a sevenϪmembered ring has little effect also on the bite
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G. B. Deacon, P. W. Elliott, A. P. Erven, G. Meyer
Table 2 Selected bond distances and angles in complexes 1Ϫ8 /pm, °
1
2
3
4
5
6
7
8
Mol. A Mol. B
PtϪC51
PtϪCl
PtϪP1
PtϪP2
208(1)
209.4(6) 206.8(7) PtϪC51
203(1)
200(1)
201(1)
202(1)
207.4(7) 206.5(8) PtϪCl1
205.9(7) PtϪCl2
235.9(2) 236.2(1)
235.9(2)
223.9(2) 225.0(1)
225.4(1)
236.8(3) 237.0(1) 235.9(2) PtϪC61
221.9(3) 222.9(2) 224.5(2) PtϪP1
227.8(3) 231.4(1) 230.8(2) PtϪP2
228.1(3) 227.4(3) 230.4(2) 231.0(2) PtϪP1
227.0(3) 227.4(3) 229.9(2) PtϪP2
P1ϪC1
P1ϪC11
P1ϪC21
P2ϪC2/3/4
P2ϪC31
P2ϪC41
C1ϪC2
C2ϪC3
C3ϪC4
C51ϪPtϪP1
C51ϪPtϪP2
P1ϪPtϪP2
C51ϪPtϪCl
P1ϪPtϪCl
P2ϪPtϪCl
C1ϪP1ϪPt
C2/3/4ϪP2ϪPt
C2ϪC1ϪP1
183(1)
180(1)
181(1)
183.1(6) 183.9(8) P1ϪC1
182.1(5) 182.3(7) P1ϪC11
182.0(6) 183.3(7) P1ϪC21
181.8(9) 183(1)
182.2(7) 183.4(5)
179.8(7) 182.3(6)
181.6(7) 181.3(6)
186.2(6)
181.8(6)
182.6(6)
153.5(7) 154.3(9)
150.4(9)
179(1)
180(1)
183(1)
179(1)
182(1)
152(1)
178(1)
178(1)
185.7(9) 182.9(7)
178(1)
180(1)
152(2)
182.5(9) 181.3(6) 182.2(7) P2ϪC2/3
180(1)
182(1)
154(1)
181.9(6) 182.0(7) P2ϪC31
181.3(6) 183.2(7) P2ϪC41
153.0(8) 151(2)
152.3(9) 146(2)
152(1)
C1ϪC2
C2ϪC3/2a)
C1a)ϪC2a)
C51ϪPtϪP1
153(1)
151.5(8) C3ϪC4
91.8(2) 92.1(3) 88.9(2) 88.6(2) P1ϪPtϪCl1
149.3(8)
90.05(7) 85.59(5)
90.4(3) 90.8(2)
90.9(2)
174.0(3) 173.5(2) 172.9(2) C51ϪPtϪP2/1a)
176.7(3) 176.8(3) 176.7(2) 175.1(2) P1b)2ϪPtϪCl1 175.86(7) 179.04(5)
85.8(1) 93.79(5) 95.66(6) P1ϪPtϪP2/1a)
85.1(1) 85.2(1) 94.07(6) 96.3(1) P1ϪPtϪP2
91.91(9) 95.37(5)
90.7(3) 85.8(2)
86.0(2)
C51ϪPtϪC61/51a)
90.5(3) 87.7(4) 87.2(2) 86.6(4) Cl1ϪPtϪCl2/1b) 87.8(1)
87.83(5)
170.17(6)
91.21(5)
178.3(1) 173.21(6) 176.88(7) C61ϪPtϪP1
93.0(1) 90.11(5) 87.45(6) C61ϪPtϪP2
108.8(4) 116.4(2) 117.5(2) C1ϪP1ϪPt
107.2(4) 115.0(2) 120.0(2) C2/3/1a)ϪP2/1a)ϪPt
107.9(7) 113.8(4) 119.4(8) C2ϪC1ϪP1
177.5(3) 178.8(4) 174.2(2)
92.5(3) 95.0(3) 90.0(2)
107.2(3) 107.2(3) 117.1(3) 119.3(2) C1ϪP1ϪPt
107.2(3) 107.6(3) 115.9(2) 119.3(2) C4ϪP2ϪPt
108.5(7) 108.1(7) 114.4(5) 117.8(4) C2ϪC1ϪP1
116.6(2) 118.3(2)
116.6(2)
115.3(6) 113.9(4)
119.2(4)
C1/2/3ϪC2/3/4ϪP2 108.1(7) 117.8(4) 115.4(5) C1/2/2a)ϪC2/3/1a)ϪP2/1a) 107.7(7) 106.9(7) 112.7(5) 117.8(4) C3ϪC4ϪP2
C1ϪC2ϪC3
113.1(5) 120(1)
C1ϪC2ϪC3/2a)
114.4(9) 115.0(5)
a) Transformations of the asymmetric unit: 1Ϫx, y, Ϫz
b) Transformations of the asymmetric unit: x, 0.5Ϫy, z
Fig. 5 Disordered carbon chain of cis-[PtCl(C6F5)(dppp)] (3).
With respect to intraϪ and interϪmolecular packing,
there is
a tendency for the phenyl rings of the
Ph2P(CH2)nPPh2 (n ϭ 2Ϫ4) ligands and the C6F5 groups
to cut the coordination plane at a similar angle (Fig. 4).
For the dichlorides cisϪ[PtCl2L] (L ϭ dppe [13], dppp [14]),
7 and 8, 3, 4 and 4 groups respectively meet this criterion.
With 4Ϫ6 new motifs appear. Not only are all six rings
orthogonal to the coordination plane but two near linear
PhϪPϪPtϪC6F5 alignments are evident in each, with the
structural regularity least for 4. This pattern is also found
in 1Ϫ3, where 1 has two rings orthogonal, 2 has three, and
3 has five rings cutting the coordination plane though not
at 90° but at 70°. There is evidence that solvation upsets the
regularity of the structures. For example in the pairs 5 and
5 · 2 C3H6O and cisϪ[PtCl2(dppp)] and 7, less rings are
Fig. 4 Unit cell cis-[Pt(C6F5)2(dppp)] (5), view along [001].
angle and is evidently accommodated by the flexibility of
the alkane chain.
Bond lengths of 4Ϫ6 are similar to corresponding re-
ported distances for cisϪ[Pt(C6F5)2P2] complexes including
bridged dimers [23Ϫ25]. Apart from the dppe complexes,
the PtϪC distances are unaffected by the number of C6F5
groups.
846
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Z. Anorg. Allg. Chem. 2005, 631, 843Ϫ850

1,nϪBis(diphenylphosphino)alkane(pentafluorophenyl)-platinum(II) Complexes
spectrometer. NMR spectra were obtained on a Bruker DPX300
orthogonal for the solvates than the unsolvated species.
Thus, the unusual intersection angles of 3 may arise from
solvation. Evidence of steric stress in 2, 3, 5 and 6 is pro-
vided by one or two close ipsoϪC(Ph) ··· ipsoϪC(C6F5) ap-
proaches (306Ϫ326 pm), which are well within the sum of
two aryl van der Waals radii (346 pm) [26]. The correspond-
ing values for 1 and 4 are larger (334Ϫ362 pm) as the aro-
matic rings are laterally displaced from each other. In the
closest approach (3) the two rings are adjacent but diver-
gent. In 1Ϫ6 phenyl rings are located above and below dif-
ferent PtϪP bonds such that orthoϪhydrogen atoms (calcu-
lated positions) are situated above and below the platinum
atom at 288Ϫ306 pm, essentially corresponding to the sum
of the van der Waals radii of platinum and hydrogen
(295 pm) [26, 27]. Uniquely in 6, the C2ϪC2* bond lies
aligned with the coordination plane.
There are close intermolecular contacts between hydro-
gen atoms (in calculated positions) and fluorine (227 pm)
and chlorine (278 pm) respectively, which are smaller than
the sum of the van der Waals radii (290 pm and 320 [26])
and are not sufficiently close to be indicative of possible
HϪbonding interactions. The alignment of phenyl rings ex-
tend through the crystal structure, quite spectacularly so for
5 (Fig. 4).
spectrometer. The complexes were dissolved in deuterochloroform.
1H and 19F NMR spectra are referenced to internal TMS and
CFCl3 respectively; the chemical shifts for the 31P spectra are rela-
tive to external H3PO4 and P atoms are numbered as in the
XϪray diagrams.
Decarboxylation procedure
The dichlorobisdiphenylphosphinealkane platinum(II) complexes
and thallium(I) pentafluorobenzoate were mixed in 10 ml of dry
pyridine and heated under reflux. The reactions were carried out
under a slow nitrogen stream which was passed through a saturated
barium hydroxide solution. The extent of decarboxylation (%CO2)
was gravimetrically determined as precipated barium carbonate
and expressed as a percentage of total available CO2. On com-
pletion of reaction, the pyridine was removed under vacuum at
room temperature and the resultant residue washed with hexane
(ϳ30 ml). Extraction of the residue with boiling acetone (100 ml),
filtration to remove thallium(I) chloride or insoluble impurities,
and evaporation of the filtrate to dryness gave the organoplatinum
complex. Amounts of reagents and yields are given in Table 1. The
mixture of cisϪ[Pt(C6F5)2 (dppp)] and cisϪ[PtCl(C6F5)(dppp)]
(Table 1) was separated by preparative TLC on Kieselgel with
CHCl3/CCl4 as eluent; column chromatography on Al2O3 with ace-
tone/hexane (1:3.5) as eluent is also possible. TLC on neutral Al2O3
with the same eluent was used after all reactions to determine
whether a single product was obtained.
Conclusions
cis؊[PtCl(C6F5)(dppe)] (1): C32H24ClF5P2Pt (796.0 g/mol); M.p.:
251Ϫ253 °C; C 48.3 (calc. 48.3); H 2.9 (3.0); Cl 4.1 (4.5); F 12.2
(11.9) %.
Pentafluorphenyl substituted diphosphine platinum(II)
complexes cisϪ[PtXYL] (X ϭ Cl or C6F5, Y ϭ C6F5, L ϭ
dppe, dppp, dppb) are obtained in high yields with short
reaction times by decarboxylation reactions. The XϪray
crystal structures of these compounds and the reported di-
chloro substituted precursors show monomeric chelating
complexes with cis geometry indicating that a seven mem-
bered chelate ring is preferred over a bridging dimeric ar-
rangement for all three dppb complexes.
IR cmϪ1: 1499 vs, 1483 m(sh), 1454 vs, 1437 vs, 1354 m, 1105 s, 1067 m,
1053 s, 955 vs, 881 m, 824 m, 785 m, 748 m, 716 s, 706 s, 690 vs, 536 vs, 490 s,
440 m. MS (m/z) (%): ESMS(ϩ): 1614 (40) [2MϪClϩC3H6O / 2MϩNa]ϩ,
1210 (15), 877 (20) [MϩNaϩC3H6O]ϩ, 853 (20) [MϩKϩH2O]ϩ, 835 (15)
[MϩK]ϩ, 818 (100) [MϪClϩC3H6O]ϩ, 804 (20) [PtO2CC6F5 (dppe)]ϩ, 760
(15) [MϪCl]ϩ; MS(EI): 796 (10) [Mϩ], 761 (10) [PtH(C6F5)dppeϩ], 629 (45)
[PtCldppeϩ], 593 (100) [Ptdppeϩ], 565 (20) [Pt(Ph2P)2ϩ], 303 (40) [Pt(PhP)ϩ].
1H NMR: δ ϭ 2.03Ϫ2.16 (m, 1 H, CH2), 2.18Ϫ2.30 (m, 1 H, CH2),
2.31Ϫ2.61 (m, 2 H, CH2), 7.30Ϫ7.41 (m, 4 H, Ph), 7.43Ϫ7.62 (m, 12 H, Ph),
7.84Ϫ8.03 (m, 4 H, Ph). 19F NMR: δ ϭ Ϫ119.3 (m with 195Pt satellites
3J(Pt,F) 268 Hz, 2 F, F(2,6)), Ϫ162.3 (m, 1 F, F(4)), Ϫ164.3 (m, 2 F, F(3,5)).
31P NMR: δ ϭ 39.78 (d, J(P,P) 7 Hz, with 195Pt satellites 1J(Pt,P) 3720 Hz,
1 P, P(1)), 40.95 (m with 195Pt satellites 1J(Pt,P) 2251 Hz, 1 P, P(2)). From
one preparation, colourless single crystals of cisϪ[PtCl(C6F5)(dppe)] · 0.5 py
(1) were grown, but single crystals of the unsolvated species could not be ob-
tained.
Experimental Part
General
All reactions were carried out under dry nitrogen using standard
Schlenk techniques. Pyridine was dried by distillation from potass-
cis؊[PtCl(C6F5)(dppp)] (2): C33H26ClF5P2Pt (810.0 g/mol); M.p.:
312Ϫ314 °C (dec.); C 48.6 (calc. 48.9); H 3.4 (3.2); Cl 4.4 (4.4); F
11.7 (11.7) %.
ium
hydroxide.
Commercial
Ph2P(CH2)2PPh2(dppe),
Ph2P(CH2)3PPh2(dppp) and Ph2P(CH2)4PPh2(dppb) of >95 % pu-
rity were from Strem. The dichlorophosphine complexes were pre-
pared as reported [28] and worked up by treatment with boiling
ethanolϪhydrochloric acid [29]. TlO2CC6F5 was prepared as de-
scribed [15]. Elemental analyses (C, H, F, Cl) were determined by
the Australian Microanalytical Service, Melbourne, Australia and
(C, H) by the Institut für Anorganische Chemie der Universität zu
Köln, Germany. Infrared spectra were recorded with a Bruker IFS
66v/S instrument within the range of 4000Ϫ400 cmϪ1. The spectra
were obtained with KBr discs of the compounds. Weak and very
weak IR bands have been omitted. Electrospray mass spectra were
obtained using a Micromass Platform benchtop QMS with electro-
spray source or Bruker BioApec 47e FTMS with 4.7 T supercon-
ducting magnet and fitted with an Analytica electrospray source.
Electron impact spectra were obtained on a VG Micromass 7070F
IR cmϪ1: 1499 vs, 1485 m, 1456 vs, 1437 vs, 1414 m, 1358 m, 1153 m, 1103 s,
1068 m, 1055 s, 972 m, 955 vs, 837 m, 789 s, 744 s, 714 m(sh), 698 vs, 669 s,
532 m, 513 vs, 503 s, 482 m. MS (m/z) (%): ESMS(Ϫ): 1655 (40) [2MϩCl]Ϫ,
845 (100) [MϩCl]Ϫ; MS(EI): 810 (<1 %) [Mϩ], 774 (8) [Pt(C6F5)dpppϩ],
643 (10) [PtCldpppϩ], 607 (100) [Ptdpppϩ], 565 (10) [Pt(Ph2P)2ϩ], 380 (10)
[Pt(Ph2P)ϩ], 303 (40) [Pt(PhP)ϩ]. 1H NMR: δ ϭ 1.85Ϫ2.16 (m, 2 H, CH2),
2.24Ϫ2.56 (m, 2 H, CH2), 2.59Ϫ2.95 (m, 2 H, CH2), 7.10Ϫ7.22 (m, 4 H, Ph),
7.27Ϫ7.54 (m, 12 H, Ph), 7.68Ϫ7.84 (m, 4 H, Ph). 19F NMR: δ ϭ Ϫ119.4
(m with 195Pt satellites 3J(Pt,F) 274 Hz, 2 F, F(2,6)), Ϫ163.2 (m, 1 F, F(4)),
Ϫ164.4 (m, 2 F, F(3,5)). 31P NMR: δ ϭ Ϫ3.82 (d, J(P,P) 28 Hz, with 195Pt
satellites 1J(Pt,P) 3603 Hz, 1 P, P(1)), Ϫ4.09 (m with 195Pt satellites 1J(Pt,P)
2072 Hz, 1 P, P(2)).
cis؊[PtCl(C6F5)(dppb)] (3): Isolated as acetone solvate (see X-ray
structure, Table 2 and 3) C34H28ClF5P2Pt · C3H6O (882.1 g/mol);
M.p.: 267Ϫ269 °C; C 50.36 (calc. 50.38); H 3.84 (3.88) %.
Z. Anorg. Allg. Chem. 2005, 631, 843Ϫ850
zaac.wiley-vch.de
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
847

G. B. Deacon, P. W. Elliott, A. P. Erven, G. Meyer
Table 3 Crystal data and structure refinement for 1Ϫ3, 7 and 8
1a)
2
3
7
8
Crystal data
Empirical formula
Colour, habit
Crystal size mm
Crystal system,
Space group
a /pm
C34.5H24ClF5N0.5P2Pt
Colourless, block
0.25 x 0.17 x 0.15
C33H26ClF5P2Pt
Colourless, block
0.21 x 0.17 x 0.16
monoclinic, P21/n
C37H34ClF5OP2Pt
Colourless, block
0.20 x 0.14 x 0.13
monoclinic, P21/n
C28H28Cl4P2Pt
C28H28Cl2P2Pt
Colourless, needles
0.72 x 0.09 x 0.08
orthorhombic, Pnma
Colourless, block
0.10 x 0.10 x 0.08
¯
¯
triclinic, P1
triclinic, P1
842.3(2)
1426.1(3)
1432.5(3)
101.53(2)
94.36(2)
103.43(2)
1626.3(6), 2
833.02
1351.5(2)
1541.6(2)
1541.1(2)
90.00
106.57(2)
90.00
3077.5(7), 4
810.02
1.748
1236.4(2)
2272.9(4)
1383.8(2)
90.00
113.17(1)
90.00
3575.0(9), 4
882.12
1.639
1215.11(8)
1535.8(1)
1588.9(2)
90.00
90.00
90.00
2965.2(4), 4
763.33
1.710
5.217
1488
870.5(1)
1080.6(2)
1454.3(2)
87.01(2)
78.85(2)
72.65(2)
1281.1(3), 2
692.43
b /pm
c /pm
α /°
β /°
γ /°
Volume /106 pm3, Z
FW, g/mol
ρ (calc.), g/cm3
μMo /mmϪ1
F(000)
1.701
4.548
809
1.795
5.826
676
4.803
1576
4.144
1736
Data Collection
2θmax
°
50
23804
50
21654
50
25319
50
32676
48.08
10189
Nt
N
5717
0.1514, 0.1887
3281
5389
0.0620, 0.0640
3667
6031
0.0771, 0.0724
4075
2718
0.1257, 0.0470
2261
3767
0.0318, 0.0308
3414
Rint, Rσ
No
Absorption correction
TЈmin,max
numerical
0.411, 0.506
numerical
0.390, 0.464
numerical
0.503, 0.583
numerical
0.575, 0.659
numerical
0.564, 0.627
Solution and Refinement
Number of parameters refined
Final R indices (obs. data)
397
379
436
158
298
R ϭ 0.0477,
wR ϭ 0.0632
R ϭ 0.1042,
wR ϭ 0.0773
0.712
R ϭ 0.0332
wR ϭ 0.0583
R ϭ 0.0596
wR ϭ 0.0629
0.867
R ϭ 0.0354
wR ϭ 0.0724
R ϭ 0.0655
wR ϭ 0.0786
0.928
R ϭ 0.0476
wR ϭ 0.1116
R ϭ 0.0564
wR ϭ 0.1152
1.019
R ϭ 0.0263
wR ϭ 0.0.635
R ϭ 0.0305
wR ϭ 0.0650
1.062
Final R indices (all data)
GoodnessϪofϪfit
CCDC No.
253563
253565
253560
253566
253561
a) Hydrogen atoms of pyridine solvent have not been calculated owing to disorder.
IR cmϪ1: 1678 vs(br), 1499 vs, 1485 m, 1456 vs, 1437 vs, 1387 m, 1358 m,
1101 s, 1055 s, 955 vs, 908 m, 820 m, 785 m, 741 s, 714 m, 692 vs, 658 m,
530 m, 563 s, 484 m, 436 m. MS (m/z) (%): ESMS(Ϫ): 937 (20)
[MϩO2CCF3]Ϫ, 883 (50) [MϩO2CCH3]Ϫ, 869 (50) [MϩO2CH]Ϫ, 859 (100)
[MϩCl]Ϫ. 1H NMR: δ ϭ 1.50Ϫ1.65 (m, 2 H, CH2) (observed in d6Ϫacetone,
obscured by H2O In CDCl3), 2.05Ϫ2.29 (m, 8 H, CH2 and C3H6O),
2.31Ϫ2.58 (m, 2 H, CH2), 2.66Ϫ2.91 (m, 2 H, CH2), 7.15Ϫ7.25 (m, 4 H, Ph),
7.30Ϫ7.53 (m, 12 H, Ph), 7.68Ϫ7.79 (m, 4 H, Ph). 19F NMR: δ ϭ Ϫ119.5
(m with 195Pt satellites 3J(Pt,F) 286 Hz, 2 F, F(2,6)), Ϫ163.4 (m, 1 F, F(4)),
Ϫ164.4 (m, 2 F, F(3,5)). 31P NMR: δ ϭ 20.72 (d, J(P,P) 21 Hz, with 195Pt
satellites 1J(Pt,P) 3861 Hz, 1 P, P(1)), Ϫ0.44 (m with 195Pt satellites 1J(Pt,P)
2083 Hz, 1 P, P(2)).
[MϩO2CH]Ϫ, 977 (65) [MϩCl]Ϫ, 972 (40) [MϩOCH3]Ϫ; MS(EI): 774 (<1 %)
[Pt(C6F5)dpppϩ], 607 (100) [Ptdpppϩ], 565 (10) [Pt(Ph2P)2ϩ] and 303 (50)
[Pt(PhP)ϩ]. 1H NMR: δ ϭ 1.91Ϫ2.19 (m, 2 H, CH2), 2.69Ϫ2.92 (m, 4 H,
CH2), 7.19Ϫ7.36 (m, 12 H, Ph), 7.37Ϫ7.49 (m, 8 H, Ph). 19F NMR: δ ϭ
Ϫ117.4 (m with 195Pt satellites 3J(Pt,F) 329 Hz, 4 F, F(2,6)), Ϫ163.7 (m, 2 F,
F(4)), Ϫ164.6 (m, 4 F, F(3,5)). 31P NMR: δ ϭ Ϫ4.23 (m with 195Pt satellites
1J(Pt,P) 2190 Hz, P(1,2)).
Additional to the XϪray structure of 5 a solvated species was also
crystallized: 3 · 2 C3H6O(P 21/a (No. 14), a ϭ 1211.90(2) pm, b ϭ
3032.29(2) pm, c ϭ 1287.07(3) pm, β ϭ 117.979(2)°, V ϭ 4177.0(1)
106 pm3, Z ϭ 4). Because of less satisfactory refinement param-
eters, this structure has not been deposited with CCDC.
cis؊[Pt(C6F5)2(dppe)] (4): C38H24F10P2Pt (927.6 g/mol); M.p.:
270Ϫ272 °C (lit.: 269Ϫ270 °C [16]); C 49.0 (calc. 49.2); H 2.5 (2.6);
F 20.4 (20.5) %.
cis؊[Pt(C6F5)2(dppb)] (6): C40H28F10P2Pt (955.7 g/mol); M.p.:
307Ϫ309 °C; C 50.60 (calc. 50.27); H 3.16 (2.95) %.
IR cmϪ1: 1500 vs, 1456 vs, 1437 s, 1357 m, 1105 s, 1057 vs, 955 vs, 881 m,
835 m, 824 m, 789 m, 781 m, 746 m, 715 m(sh), 706 s, 690 s, 536 vs, 486 s
values overlap with the limited reported frequencies [30]. MS (m/z) (%):
ESMS(ϩ): 1877 (20) [2MϩNa]ϩ, 1008 (20) [MϩNaϩ C3H6O]ϩ, 950 (100)
[MϩNa]ϩ; MS(EI): 760 (2) [Pt(C6F5)dppeϩ], 593 (100) [Ptdppeϩ], 579 (<1)
[Pt(Ph2P)2CH2ϩ], 565 (20) [Pt(Ph2P)2ϩ] and 303 (40) [Pt(PhP)ϩ]. 1H NMR:
δ ϭ 2.18Ϫ2.47 (m, 4 H, CH2), 7.34Ϫ7.44 (m, 8 H, Ph), 7.45Ϫ7.57 (m, 12 H,
Ph). 19F NMR: δ ϭ Ϫ118.3 (m with 195Pt satellites 3J(Pt,F) 309 Hz, 4 F,
F(2,6)), Ϫ162.9 (m, 2 F, F(4)), Ϫ164.7 (m, 4 F, F(3,5)). 31P NMR: δ ϭ 43.15
(m with 195Pt satellites 1J(Pt,P) 2303 Hz, P(1,2)).
IR cmϪ1: 1499 vs, 1458 vs, 1437 vs, 1414 m, 1358 m, 1101 s, 1057 vs, 1047
s(sh), 1000 m, 958 vs, 901 m, 819 s, 791 s, 777 s, 750 vs, 739 vs, 698 vs, 690 vs,
658 s, 511 vs, 496 vs, 434 m. ESMS(Ϫ): 1946 (20) [2MϩCl]Ϫ, 1100 (15)
[MϩO2CCF3ϩMeOH]Ϫ, 1068 (20) [MϩO2CCF3]Ϫ, 1017 (25), 1000 (40)
[MϩO2CH]Ϫ, 991 (100) [MϩCl]Ϫ; ESMS(Ϫ)(sample diluted x5): 1946 (3)
[2MϩCl]Ϫ, 1100 (40) [MϩO2CCF3ϩMeOH]Ϫ, 1068 (65) [MϩO2CCF3]Ϫ,
1017 (45), 1000 (100) [MϩO2CH]Ϫ, 990 (85) [MϩCl]Ϫ. 1H NMR: δ ϭ
1.68Ϫ1.89 (m, 4 H, CH2), 2.61Ϫ2.86 (m, 4 H, CH2), 7.28Ϫ7.38 (m, 8 H, Ph),
7.39Ϫ7.52 (m, 12 H, Ph). 19F NMR: δ ϭ Ϫ117.8 (m with 195Pt satellites,
3J(Pt,F) 310 Hz, 4 F, F(2,6)), Ϫ163.5 (m, 2 F, F(4)), Ϫ164.6 (m, 4 F, F(3,5)).
31P NMR: δ ϭ 10.00 (m with 195Pt satellites 1J(Pt,P) 2307 Hz, P(1,2)).
cis؊[Pt(C6F5)2(dppp)] (5): C39H26F10P2Pt (941.6 g/mol); M.p.:
>325 °C; C 49.4 (calc. 49.7); H 2.6 (2.8); F 20.1 (20,2.9) %.
IR cmϪ1: 1500 vs, 1456 vs, 1437 s, 1358 m, 1153 m, 1103 s, 1057 vs, 974 m,
957 vs, 835 m, 792 s, 781 m, 754 m, 741 s, 704 s, 690 s, 665 s, 519 vs, 497 s.
MS (m/z) (%): ESMS(ϩ): 1905 (30) [2MϩNa]ϩ, 1022 (25) [MϩNaϩ
C3H6O]ϩ, 964 (100) [MϩNa]ϩ; ESMS(Ϫ):1995 (20) [2MϩO2CCF3]Ϫ, 1945
(15) [2MϩOMeϩMeOH]Ϫ, 1927 (15) [2MϩO2CH]Ϫ, 1918 (40) [2MϩCl]Ϫ,
1054 (100) [MϩO2CCF3]Ϫ, 1004 (20) [MϩOMeϩMeOH]Ϫ, 986 (40)
X؊ray crystal structure analyses
Colourless single crystals of good XϪray quality were grown by
slow evaporation of a solution of the crude product in acetone
(1Ϫ6, 8) or dichloromethane (7).
848
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2005, 631, 843Ϫ850

1,nϪBis(diphenylphosphino)alkane(pentafluorophenyl)-platinum(II) Complexes
Table 4 Crystal data and structure refinement for bis pentafluorophenyl complexes 4Ϫ6
4
5
6
Crystal data
Empirical formula
Colour, habit
Crystal size /mm
Crystal system,
Space group
a /pm
C38H24F10P2Pt
C39H26F10P2Pt
Colourless, block
0.38 x 0.19 x 0.15
tetragonal, P43
C40H28F10P2Pt
Colourless, block
0.20 x 0.16 x 0.15
monoclinic, P21/c
Colourless, needle
0.27 x 0.17 x 0.13
monoclinic, C2
1858.1(3)
1878.2(2)
2131.1(3)
90.00
109.48(2)
90.00
7012(2), 8
927.60
1.757
1492.0(2)
1492.0(2)
1628.4(2)
90.00
90.00
90.00
3625.1(7), 4
941.63
1.725
4.039
1832
1680.8(2)
1011.5(2)
1108.6(1)
90.00
109.02(1)
90.00
1781.8(4), 2
955.65
1.781
b /pm
c /pm
α /°
β /°
γ /°
Volume /106 pm3, Z
FW g/mol
ρ (calc.) g/cm3
μMo /mmϪ1
F(000)
4.174
3600
4.110
932
Data Collection
2θmax
°
50
58657
50
21793
50
6320
Nt
N
11753
0.1583, 0.1841
5402
6157
0.0595, 0.0586
5043
3127
0.0342, 0.0301
3123
Rint, Rσ
No
Absorption correction
TЈmin,max
numerical
0.453, 0.535
numerical
0.414, 0.546
numerical
0.437, 0.586
Solution and Refinement
Number of parameters refined
Final R indices (obs. data)
919
469
240
R ϭ 0.0433
wR ϭ 0.0552
R ϭ 0.1204
wR ϭ 0.0689
0.714
R ϭ 0.0279
wR ϭ 0.0531
R ϭ 0.0408
wR ϭ 0.0558
0.915
Ϫ0.021(6)
253564
R ϭ 0.0214
wR ϭ 0.0516
R ϭ 0.0217
wR ϭ 0.0517
1.040
Final R indices (all data)
GoodnessϪofϪfit
FlackϪx
CCDC No.
253562
253559
Diffraction intensities from small single crystals (in sealed glass
capillaries) were measured with image plate diffractometers (IPDS
Table 2. Figs. 1Ϫ5 pictures were made with the aid of the program
DIAMOND [35].
I
or II, Stoe) at room temperature. Data acquisition:
Hydrogen atoms of the pyridine solvent in 1 have not been calcu-
lated due to high thermal parameters. In 3 the atom C2 of the
ligand’s carbon chain is disordered with occupation 50.5 % for C2A
and 49.5 % for C2B owing to a disorder of the hydrogen atoms of
C1A/B and C3A/B (Fig. 5).
MoϪKαϪradiation (graphite monochromator, λ ϭ 71.07 pm);
Δϕ ϭ 2°; detector distance: 60 mm (1Ϫ6) and 80 mm (7 and 8);
ϕ ϭ 0Ϫ200° (2, 3, 5 and 6), 0Ϫ250° (4 and 8), 0° Յ ω Յ 180° (ϕ ϭ
0°, Δω ϭ 2°) and 0° Յ ω Յ 180° (ϕ ϭ 90°, Δω ϭ 2°) (1 and 7);
irradiation time: 5 min (4), 4 min (1), 3 min (2, 3, 5, 6 and 8) and
2.6 min (7). Numerical absorption corrections were applied to the
data by the programs XϪRED and XϪSHAPE [31, 32]. The struc-
tures were solved by conventional methods and refined with aniso-
tropic thermal parameter for the nonϪhydrogen atoms (except of
the disordered pyridine solvent in cisϪ[PtCl(C6F5)(dppe)] which
was refined with isotropic thermal parameters) using the SHELX
97 software package [33, 34]. All hydrogen atoms were located in
Acknowledgement. We are grateful to Fritz-ter-Mer-Stiftung, Studi-
enstiftung des deutschen Volkes, Verband der Chemischen Indus-
trie and the Australian Research Council for support.
References
[1] G. B. Deacon, S. J. Faulks, G. N. Pain, Adv. Organomet. Chem.
1986, 25, 237.
[2] Yu. A. Ol’dekop, N. A. Maier, Synthesis of Organometallic
Compounds by Decarboxylation of Metal Acylates, Science and
Technology, Minsk 1976.
[3] R. C. Larock, Organomercury Compounds in Organic Syn-
thesis, Springer Verlag, Berlin & N. Y. 1985, p. 101.
[4] J. J. Zuckermann, Inorganic Reactions and Methods, Vol. II,
VCH, NY 1985, pp 326Ϫ331.
[5] E. W. Abel, F. G. A. Stone, G. Wilkinson, Comprehensive Or-
ganometallic Chemistry II, Vol. 8 J. D. Atwood (eds), Vol. 9 R.
J. Puddephatt (eds), Pergamon Oxford 1995.
difference maps; not all would refine meaningfully in (x, y, z, Uiso
so all were constrained in these parameters in the final refinement
cycles.
)
Crystallographic data for the structures have been deposited with
the Cambridge Crystallographic Data Centre, for CCDC numbers
see Tables 3 and 4. Copies of the data can be obtained free of
charge on application to The Director CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (Fax: ϩ44 (1223)336Ϫ033; e-mail for
inquiry: fileserv@ccdc.cam.ac.uk; email for deposition: deposit@-
ccdc.cam.ac.uk).
Crystal and refinement parameters for mono- (1Ϫ3) and bis-penta-
fluorophenyl (4Ϫ6) substituted and dichloro (7, 8) complexes are
listed in Table 3 and 4, with selected bond distances and angles in
[6] A. L. Poznyak, V. E. Stel’mashok, Koord. Khim. 1979, 5, 1670;
Chem. Abstr. 1980, 93, 17708d; V. I. Pavlovski, A. L. Poznyak,
Z. Anorg. Allg. Chem. 2005, 631, 843Ϫ850
zaac.wiley-vch.de
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
849

G. B. Deacon, P. W. Elliott, A. P. Erven, G. Meyer
Dokl. Akad. Nauk BSSR 1980, 24, 1103; Chem. Abstr. 1981,
94, 112411g; V. E. Stel’mashok, A. L. Poznyak, Russ. J. Inorg.
Chem. 1984, 26, 1324; A. L. Poznyak, V. I. Pavlovski, Z. Chem.
1981, 21, 74; A. L. Poznyak, V. I. Pavlovski, Russ. J. Inorg.
Chem. 1981, 26, 292; A. L. Poznyak, V. I. Pavlovski, E. B.
Chuklanova, T. N. Polynova, M. A. PoraiϪKoshits, Mh.
Chem., 1982 113, 561; A. L. Poznyak, V. I. Pavlovski, Z.
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