Concentration dependent switch from addition to substitution in the reaction between salicylaldoxime and a nitrile platinum(IV) complex

Article abstract of DOI:10.1016/S0020-1693(02)00867-8

The nitrile complex [Ph₃PCH₂Ph][PtCl₅(EtCN)] reacts with one equivalent of salicylaldoxime, HON=CH(C₆H₄OH-o), in CH₂Cl₂ to afford mainly the addition product [Ph₃PCH₂Ph][PtCl₅{NH=C(Et)ON=CH(C ₆H₄OH-o)}] (1). In a diluted solution, i.e. if the same amount of the reagents is dissolved in 50-fold volume of dichloromethane, the four platinum-containing species, i.e. 1, [Ph₃PCH₂Ph][PtCl₄{C₆H ₄(O)C(H)=NOH}] (2) [Ph₃PCH₂Ph][PtCl₅(NH₃)] (3), and [Ph₃PCH₂Ph]₂[PtCl₆] (4), are formed and the substitution compound 2 is the major product at low concentrations. Addition of EtCN to the less concentrated solution suppresses the formation of the substitution product 2 and moves the reaction back towards formation of the addition product 1. The complex 1 is unstable in non-dried solutions and decomposes to give 2 along with 3, 4 and EtCO₂H. Compounds 1, 2 and 4·1/2H₂O were characterized by elemental analyses, FAB mass-spectrometry, IR and ¹H, ¹³C{¹H}, ³¹P{¹H} and ¹⁹⁵Pt NMR spectroscopies. X-ray structure determinations have been performed for 2 and 4·1/2H₂O.

Full text of DOI:10.1016/S0020-1693(02)00867-8

Inorganica Chimica Acta 336 (2002) 95ꢀ100
/
www.elsevier.com/locate/ica
Concentration dependent switch from addition to substitution in the
reaction between salicylaldoxime and a nitrile platinum(IV) complex
Nadezhda A. Bokach a,c, Matti Haukka b, Armando J.L. Pombeiro a,*,
Svetlana N. Morozkina c, Vadim Yu. Kukushkin c,*
a Centro de Qu´mica Estrutural, Complexo I, Instituto Superior Te´cnico, Av. Rovisco Pais, 1049-001 Lisbon, Portugal
b Department of Chemistry, University of Joensuu, PO Box 111, FIN-80101 Joensuu, Finland
c Department of Chemistry, St. Petersburg State University, 198904 Stary Petergof, Russian Federation
Received 7 January 2002; accepted 18 February 2002
Abstract
The nitrile complex [Ph3PCH2Ph][PtCl5(EtCN)] reacts with one equivalent of salicylaldoxime, HONÄ
to afford mainly the addition product [Ph3PCH2Ph][PtCl5{NHÄC(Et)ONÄCH(C6H4OH-o)}] (1). In a diluted solution, i.e. if the
same amount of the reagents is dissolved in 50-fold volume of dichloromethane, the four platinum-containing species, i.e. 1,
[Ph3PCH2Ph][PtCl4{C6H4(O)C(H)ÄNOH}] (2) [Ph3PCH2Ph][PtCl5(NH3)] (3), and [Ph3PCH2Ph]2[PtCl6] (4), are formed and the
/CH(C6H4OH-o), in CH2Cl2
/
/
/
substitution compound 2 is the major product at low concentrations. Addition of EtCN to the less concentrated solution suppresses
the formation of the substitution product 2 and moves the reaction back towards formation of the addition product 1. The complex
1 is unstable in non-dried solutions and decomposes to give 2 along with 3, 4 and EtCO2H. Compounds 1, 2 and 4×
characterized by elemental analyses, FAB mass-spectrometry, IR and 1H, 13C{1H}, 31P{1H} and 195Pt NMR spectroscopies. X-ray
structure determinations have been performed for 2 and 4×1/2H2O. # 2002 Elsevier Science B.V. All rights reserved.
/1/2H2O were
/
Keywords: Nitrile complexes; Platinum(IV) complexes; Nucleophilic addition; Substitution; Hydrolysis; Metal-mediated reactions
1. Introduction
been discovered fairly recently a remarkable addition of
oximes HONÄ
CR1R2, to coordinated nitriles in
[PtCl4(RCN)2] to give the iminoacylated products
[PtCl4{HNÄC(R)ONÄ 10]. This reaction
CR1R2}2] [6ꢀ
was later also found to occur in rhodium(III) [11],
rhenium(IV) [12] and platinum(II) systems [13]; in the
latter case the platinum(II)-assisted addition to dialkyl-
cyanamides is catalyzed by Lewis acids. The useful
/
Metal-mediated transformations of organonitriles
play an important role in both laboratory and industry
due to their well-recognized chemical versatility and
possibility to achieve products of vital significance such
as, e.g. acrylamide or nicotineamide. In particular,
/
/
/
addition of nucleophiles to the CÅ
electrophilically activated by ligation to a metal center,
offers an attractive route for the creation of diverse CÃ
C, CÃN, CÃO, CÃP, and CÃS bonds (for recent reviews
see Ref. [1]). Owing to our general interest in ligand
reactivity [2ꢀ5] shared with the particular focus on
reactions of the metal-bound RCN [6ꢀ16], we carried
out a search of potential nucleophiles for couplings with
[M]ꢀNCR group, giving new functionalities, and has
/
N triple bond,
coupling was then extended to nitrones ꢁONꢂ(R3)Ä
CR1R2 [14]*
which can be viewed as the alkylated
form of the other oxime tautomer*to achieve, as a
3] cycloaddition, the platinum(IV) com-
/
/
/
/
/
/
/
/
result of [2ꢂ
/
plexes [PtCl4(D4-1,2,4-oxadiazoline)2] from which diffi-
/
cult-to-obtain D4-1,2,4-oxadiazolines were liberated.
/
Moreover, oximeꢀnitrile systems were used in the 3d
/
/
metal-mediated processes to furnish amidines [15] and to
obtain carboxamides by a catalytic and environmentally
benign route [16].
* Corresponding authors. Tel.: ꢂ
/
351-218-419 237; fax: ꢂ351-218-
/
Taking into account the high potential of the oximeꢀ
/
464 455
E-mail addresses: pombeiro@ist.utl.pt (A.J.L. Pombeiro),
kukushkin@VK2100.spb.edu (V.Y. Kukushkin).
nitrile coupling, we focused our attention on the
investigation of general features, restrictions and plau-
0020-1693/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 0 - 1 6 9 3 ( 0 2 ) 0 0 8 6 7 - 8

96
N.A. Bokach et al. / Inorganica Chimica Acta 336 (2002) 95ꢀ100
/
sible mechanism of the reaction*
/
both experimentally
CH(C6H4OH-o)}2] containing iminoacylated salicylal-
doxime [6] (the high field position of the imino H atom
suggests its involvement in hydrogen bonding (Scheme
[8] and theoretically [9]. In particular, it has been
observed that the iminoacylation is dramatically inhib-
ited by introducing acceptor groups to the oximes [8].
We have now found that the reaction can also be quite
affected by the concentration of the reagents and we
here report on the concentration dependent shift from
addition to substitution in the reaction between the
[PtCl5(EtCN)]ꢁ complex and salicylaldoxime.
1), as in other iminoacylated oximes [6ꢀ9]); (iii) ob-
/
servation of a 195Pt NMR chemical shift specific for
similar type complexes [9].
If the same amount of the reagents is dissolved in the
50-fold volume of CH2Cl2 used in the previous experi-
1
ment, the reaction mixture becomes red. H and 195Pt
NMR and TLC monitoring of products formed in the
reaction clearly indicate the formation of four platinum-
containing species, i.e. [Ph3PCH2Ph][PtCl5{NHÄ
C(Et)ONÄCH(C6H4OH-o)}] (1), [Ph3PCH2Ph][PtCl4-
{C6H4(O)C(H)ÄNOH}] (2), [Ph3PCH2Ph][PtCl5(NH3)]
/
2. Results and discussion
/
/
For the current study we addressed, on one hand, the
platinum(IV) complex [Ph3PCH2Ph][PtCl5(EtCN)] with
the highly lipophilic cation and the Et radical at the
nitrile group which provide good solubility of the
compound in dichloromethane, and on the other hand,
salicylaldoxime which can exhibit the dual reactivity in
addition to platinum-bound nitrile [6] or in substitution
around the platinum center [17]. It has been observed
that [Ph3PCH2Ph][PtCl5(EtCN)] reacts with 1 equiv. of
(3) and [Ph3PCH2Ph]2[PtCl6] (4), in variable quantities
depending on the concentration of the reaction mixture.
In the case of the more concentrated solution, the ratio
between the addition and the substitution products,
obtained by 195Pt NMR peak integration, is approxi-
mately 9:1, while in the less concentrated solution it is
almost reversed in favour of the substitution product
(approximately 8:2) and, consequently, the amount of
[Ph3PCH2Ph]2[PtCl6] (4) also increases. Moreover, addi-
tion of EtCN to the less concentrated solution sup-
presses the substitution and forwards the reaction again
to the addition route. The complexes [Ph3PCH2Ph]-
HONÄ
the yellow addition product [Ph3PCH2Ph][PtCl5{NHÄ
C(Et)ONÄCH(C6H4OH-o)}] (1) (Scheme 1) along with
/CH(C6H4OH-o) under mild conditions to afford
/
/
some other products (see below). The former compound
was purified by column chromatography. It gives
satisfactory C, H and N elemental analyses and
FABꢁ-MS and has been identified by: (i) IR spectro-
[PtCl4{C6H4(O)C(H)Ä
/
NOH}] (2), [Ph3PCH2Ph]2[PtCl6]
hemihydrate) and well-known
(4) (isolated as
a
[Ph3PCH2Ph][PtCl5(NH3)] (3) [9,18] were separated by
column chromatography and characterized by physico-
chemical methods and the former two by X-ray crystal-
lography.
scopy showing no n(CÅ
/
N) bands but displaying very
strong n(CÄ
/
N) stretch and characteristic n(NÃ
/
H)
stretching vibrations along with the strong bands due
1
to the phosphonium counterion; (ii) measuring H and
In a separate experiment it has been shown that the
13C{1H} NMR spectra where the signals due to the
addition product [Ph3PCH2Ph][PtCl5{NHÄ
/
C(Et)ONÄ
/
CH(C6H4OH-o)}] (1) is stable as solid but gradually
HNÄ
/
C moiety are in the same range as observed for the
analogous neutral complexes [PtCl4{NHÄ
/
C(Et)ONÄ
/
decomposes in solution (for instance in dichloro-
Scheme 1.

N.A. Bokach et al. / Inorganica Chimica Acta 336 (2002) 95ꢀ
/100
97
methane) giving the substitution product [Ph3PCH2Ph]-
[PtCl4{C6H4(O)C(H)ÄNOH}] (2), the hexachloride
[Ph3PCH2Ph]2[PtCl6] (4) as well as the two products
arising from the hydrolysis [9,19], i.e. [Ph3PCH2Ph]-
[PtCl5(NH3)] (3) and EtCO2H, the latter identified in 1H
NMR spectrum (Scheme 1). We believe that the con-
dissociation of the nitrile, similar to that described for
weak electrolytes by the Ostwald dilution law, increases
and, consequently the amount of ligated EtCN decreases
thus favoring the substitution via the expected dissocia-
tive mechanism. Another experimental observation
supporting this assumption is that the addition of
propanenitrile to the diluted solution suppresses the
substitution and again forwards the reaction to the
addition route.
/
version of 1, initially involves hydrolysis of the CÃ
bond of the iminoacylated ligand giving the complex
[PtCl5{NHÄ
C(Et)OH]ꢁ (having ligated carboxamide in
/O
/
the iminol form [1]) and free salicylaldoxime. The
former hydrolyses further to give 3 and EtCO2H [9],
while the liberated oxime sequests the platinum(IV)
center furnishing 2.
3. Experimental
The asymmetric unit of [Ph3PCH2Ph][PtCl4-
3.1. Materials and instrumentation
{C6H4(O)C(H)Ä
/
NOH}] (2) crystals contains a pair of
both the anionic complex and the counterion whose
bond lengths and angles are of typical values (Fig. 1,
Solvents were obtained from commercial sources and
used as received. [Ph3PCH2Ph][PtCl5(EtCN)] was ob-
tained by the published method [9] and salicylaldoxime
obtained from Aldrich. C, H and N elemental analyses
were carried out by the Microanalytical Service of the
Instituto Superior Te´cnico. M.p.s were determined on a
Kofler table. For TLC, Merck SiO2-plates silica gel 60
F254 have been used. Positive-ion FAB-MS were
obtained on a Trio 2000 instrument by bombarding 3-
nitrobenzyl alcohol (NBA) matrices of the samples with
Table 2). The salicylaldoximato(1ꢁ) ligand is coordi-
/
nated to the platinum(IV) center in its usual N,O-
bidentate mode and all bonds are of normal values well
comparable with those in the two previously reported
(salicylaldoximato) Pt(IV) complexes [17]. The anion is
additionally stabilized by hydrogen bonding between the
oxime HO group and the Cl(2) atom [H(40)Á Á ÁCl(2)
˚
˚
distance is 2.21(6) A, O(2)Á Á ÁCl(2) is 2.982(6) A, the
angle O(2)Ã
/
H(40)Á Á ÁCl(2) is 160(5)8]. The data on
8 keV (approximately 1.28ꢃ
calibration for data system acquisition was achieved
using CsI. IR spectra (4000ꢀ
400 cmꢁ1) were recorded
/
1015 J) Xe atoms. Mass
[Ph3PCH2Ph]2[PtCl6]×
/1/2H2O (4) are coherent with
many other structures of both the cation (see [20]) and
the anion (see [21,22]), although previously determined
in other combinations, and are included in Section 4.
The addition to the nitrile carbon requires strong
electrophilic activation and occurs when EtCN is bound
to the platinum(IV) center. The observed switch from
the addition to the substitution can be probably
explained on the basis of the increased amount of free
EtCN upon dilution. Indeed, in diluted solutions
/
on a BIO-RAD FTS 3000MX instrument in KBr pellets.
1H, 13C{1H}, 31P{1H} and 195Pt NMR spectra were
measured on Varian UNITY 300 and Bruker AMX 300
spectrometers at ambient temperature. 31P chemical
shifts are quoted relative to H3PO4ꢄ
chemical shifts are given relative to aq. K2[PtCl4]ꢄ
1630 ppm, half height line width are given in
parenthesis.
/
0 ppm, 195Pt
/
ꢁ
/
Fig. 1. ORTEP view of [Ph3PCH2Ph][PtCl4{C6H4(O)C(H)ÄNOH}] (1). The thermal ellipsoids are drawn at the 50% probability level.
/

98
N.A. Bokach et al. / Inorganica Chimica Acta 336 (2002) 95ꢀ100
/
3.2. Synthetic work and characterization
MS: m/z 353 [Mcation]. FABꢁ-MS: m/z 472 [Manion].
m.p.ꢄ123 8C (dec.). TLC, Rfꢄ0.52 (eluent C3H6Oꢀ
CHCl3ꢄ1:3). IR spectrum in KBr, selected bands
(cmꢁ1): 3261 m n(NÃ
H), 2923 m-w n(CÃH), 1647 s
n(CÄN), 1479 and 1433 s n(CÄC), 1107 s n(PÃC), 754 s
d(CÃ
H). 1H NMR in DMSO-d6: d 7.7 (m, Ph), 7.42 (d,
H(6) from C6H4(O)CÄ), 7.30 (t, H(4) from
C6H4(O)CÄ), 6.85 (d, H(3) from C6H4(O)CÄ) and 6.67
(t, H(5) from C6H4(O)CÄ), 5.27 (d, JPH 15.6 Hz,
CH2Ph), 6.95ꢀ7.29 (m, CH2Ph), 8.54 (sꢂd, JPtH 36.2
/
/
/
3.2.1. Concentration dependence of the reaction between
/
[Ph3PCH2Ph][PtCl5(EtCN)] and o-HOC6H4CHÄ
NOH
[Ph3PCH2Ph][PtCl5(EtCN)] (28 mg, 0.036 mmol) is
/
/
/
/
/
/
/
dissolved in dry CH2Cl2 (0.1 ml), salicylaldoxime (5 mg,
0.036 mmol) is added and the reaction mixture is left to
stand at room temperature (r.t.) for 2 days. During that
time the color of the solution gradually turns from
yellow to orange. The complexes formed are separated
by column chromatography on SiO2 (Chemapol Silica
gel L 40/100). The first fraction contains the dark-red
substitution product [Ph3PCH2Ph][PtCl4{C6H4(O)-
/
/
/
/
/
/
Hz, Ä
/
CH), 10.91 and 10.39 (s, b, OH). 31P{H} NMR in
DMSO-d6: d 28.3. 195Pt NMR in DMSO-d6: d 682 (145
Hz).
C(H)Ä
/
NOH}] (2), the addition product [Ph3PCH2Ph]-
[PtCl5{NHÄ
/
C(Et)ONÄCH(C6H4OH-o)}] (1) is in the
/
3.2.4. [Ph3PCH2Ph]2[PtCl6]×
Anal. Calc. for C50H44Cl6P2Pt×
4.04. Found: C, 53.61; H, 3.89%. FABꢂ-MS: m/z 353
[Mcation]. FABꢁ-MS: m/z 408 [Manion]. m.p.ꢄ
240 8C.
TLC, Rfꢄ0.70 (eluent C3H6OꢀCHCl3ꢄ1:1). IR spec-
trum in KBr, selected bands (cmꢁ1): 1110 s n(PÃ
C), 745
H). 31P{1H} NMR in CDCl3: d 23.3. 195Pt NMR
/
1/2H2O (4)
second one and the last fraction contains the previously
characterized [Ph3PCH2Ph][PtCl5(NH3)] (3) [9,18]. Con-
currently, [Ph3PCH2Ph]2[PtCl6] (4) in the conditions
applied retains on the silica gel but can be removed by
eluation with C3H6O. If the same amount of the
reagents is dissolved in the 50-fold volume (5 ml) of
CH2Cl2 used above, the complex [Ph3PCH2Ph][PtCl4-
/1/2H2O: C, 53.45; H,
/
/
/
/
/
s d(CÃ
/
in CD2Cl2: d 230.1 (211 Hz).
{C6H4(O)C(H)Ä
/
NOH}] (2) is mainly formed and it can
be purified by column chromatography on SiO2.
Table 1
Crystal data and structure refinement for [Ph3PCH2Ph]-
[PtCl4{C6H4(O)C(H)ÄNOH}] (2) and [Ph3PCH2Ph]2[PtCl6]×1/2H2O
(4)
3.2.2. [Ph3PCH2Ph][PtCl5{NHÄ
/
C(Et)ONÄ
/
CH(C6H4OH-o)}] (1)
Anal. Calc. for C35H34Cl5N2O2PPt: C, 45.79; H, 3.73;
N, 3.05. Found: C, 44.69; H, 3.66; N, 2.61%. FABꢂ-
MS: m/z 353 [Mcation]. FABꢁ-MS: m/z 565 [Manion], 373
2
4
Empirical formula
Formula weight
Temperature (K)
C
32H28Cl4NO2PPt
C50H45Cl6O0.50P2Pt
1123.59
150(2)
826.41
120(2)
0.71073
[PtCl5], 336 [PtCl4], 301 [PtCl3], 266 [PtCl2]. m.p.ꢄ
108 8C. TLC, Rfꢄ0.49 (eluent C3H6OꢀCHCl3ꢄ
IR spectrum in KBr, selected bands (cmꢁ1): 3285 m
n(NÃH), 1655 and 1609 s n(CÄN), 1435 s n(CÄC), 1109
s n(PÃ H). H NMR in CDCl3: d 1.31 (t,
/
105ꢀ
/
˚
Wavelength (A)
/
/
/1:3).
0.71073
monoclinic
P21/c
Crystal system
Space group
triclinic
¯
/
/
P1
/
/
/
˚
a (A)
10.6395(3)
10.6981(4)
14.4015(6)
97.087(2)
104.626(2)
97.050(2)
1553.63(10)
2
21.4101(5)
12.8386(3)
18.5806(3)
90
1
/
C), 751 s d(CÃ
/
˚
b (A)
2
7.4 Hz, 3H) and 3.32 (q, 7.4 Hz, 2H) (Et), 4.88 (d, JPH
13.9 Hz, 2H, CH2Ph), 6.98 (m, 1H), 7.07 (d, 8.4 Hz, 1H),
7.40 (t, 8.5 Hz, 1H) and 7.55 (m, 1H) (C6H4OH), 7.02
(m, 2H, ortho), 7.15 (m, 2H, meta) and 7.24 (m, 1H,
˚
c (A)
a (8)
b (8)
g (8)
114.1798(8)
90
3
˚
V (A )
Z
4659.3(2)
4
1.602
para) (CH2Ph), 7.67 (m, 12H, orthoꢂmeta) and 7.78 (m,
/
rcalc (g cmꢁ3
)
1.767
4.942
808
3H, para) (Ph), 8.38 (s, broad, 1H, NH), 8.62 (s, 1H, NÄ
/
CH). 13C{1H} NMR in CDCl3: d 10.7 (CH3) and 24.7
m (mmꢁ1
F(000)
)
3.460
2236
1
(CH2) (Et), 31.5 (CH2, JPC 47.6 Hz, CH2Ph), 117.2
(Cipso, ,
1JPC 86.0 Hz, Ph), 126.7 (Cipso 2JPC 8.3 Hz,
u Range
Index ranges
2.84ꢀ
/26.01
2.45ꢀ25.00
/
ꢁ135h 513,
ꢁ135k 513,
ꢁ175l 517
19 163
ꢁ245h 525,
ꢁ155k 515,
ꢁ225l 521
34 423
CH2Ph), 128.6 (CHp, CH2Ph), 129.0 (CHm, CH2Ph),
130.3 (CH, JPC 12.8 Hz, Ph), 131.5 (CHo, JPC 5.5 Hz,
CH2Ph), 134.4 (CH, JPC 9.1 Hz, Ph), 135.2 (CHp, Ph),
114.2, 117.7, 120.5, 132.0, 134.6 and 157.7 (C6H4OH),
Reflections collected
Independent reflections 5692
Rint
8195
0.0794
C). 31P{1H} NMR in
32.5 (400 Hz).
0.0555
158.7 (CHÄ
/
N), 176.1 (HNÄ
/
R1 [I ꢀ2s(I)]
wR2 [I ꢀ2s(I)]
wR2 (all data)
Goodness-of-fit (F2)
0.0307
0.0637
0.0677
1.039
0.0502
0.1048
CDCl3: d 23.3. 195Pt NMR in CDCl3: d ꢁ
/
0.1132
1.026
3.2.3. [Ph3PCH2Ph][PtCl4{C6H4(O)C(H)Ä
/
NOH}]
Largest difference peak 0.938 and ꢁ0.943
1.209 and ꢁ1.254
(2)
Anal. Calc. for C32H27Cl4NO2PPt: C, 46.56; H, 3.30;
N, 1.70. Found: C, 46.82; H, 3.37; N, 1.75%. FABꢂ-
ꢁ3
˚
and hole (e A
)

N.A. Bokach et al. / Inorganica Chimica Acta 336 (2002) 95ꢀ
/100
99
Table 2
compounds 2 and 4, respectively. Copies of this
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge, CB2
˚
Bond lengths (A) and angles (8) for the anion in
[Ph3PCH2Ph][PtCl4{C6H4(O)C(H)ÄNOH}] (1)
1EZ, UK (fax: ꢂ44-1223-336-033; e-mail: deposit@
/
Bond lengths
ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
Pt(1)ÃO(1)
Pt(1)ÃN(1)
Pt(1)ÃCl(1)
Pt(1)ÃCl(4)
Pt(1)ÃCl(3)
Pt(1)ÃCl(2)
C(1)ÃO(1)
O(2)ÃN(1)
N(1)ÃC(7)
C(6)ÃC(7)
1.996(3)
2.018(4)
2.3073(12)
2.3190(12)
2.3196(12)
2.3227(11)
1.334(5)
Acknowledgements
N.A.B. expresses gratitude to the International
Science Foundation (Soros Foundation) and also to
the Centro de Qu´ımica Estrutural, Complexo I, Instituto
Superior Te´cnico, Portugal, for the fellowships. A.J.L.P.
and V.Yu.K. are very much obliged to the FCT
(Foundation for Science and Technology) and the
PRAXIS XXI and POCTI programs for financial support.
V.Yu.K. thanks the PRAXIS XXI program (Portugal) for
grant BCC16428/98 and the International Science
Foundation for the Soros Professorship. The authors
thank Professors/Drs. D. Tudela, A. Ryabov and L.
Kloo for useful discussions relevant to this work.
1.380(5)
1.278(6)
1.445(7)
Bond angles
Cl(1)ÃPt(1)ÃN(1)
Cl(2)ÃPt(1)ÃO(1)
N(1)ÃPt(1)ÃO(1)
Pt(1)ÃN(1)ÃO(2)
Pt(1)ÃN(1)ÃC(7)
Pt(1)ÃO(1)ÃC(1)
Cl(1)ÃPt(1)ÃCl(2)
Cl(1)ÃPt(1)ÃCl(3)
Cl(1)ÃPt(1)ÃCl(4)
Cl(3)ÃPt(1)ÃCl(4)
178.50(11)
178.50(10)
91.64(14)
120.1(3)
125.0(3)
121.7(3)
91.72(4)
90.65(4)
90.68(4)
178.38(4)
3.2.5. X-ray structure determinations of
[Ph3PCH2Ph][PtCl4{C6H4(O)C(H)Ä
[Ph3PCH2Ph]2[PtCl6]×1/2H2O (4)
The X-ray diffraction data were collected on a Nonius
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