Synthesis, molecular structure and coordination chemistry of the first 1-aza-3,7-diphosphacyclooctanes

Article abstract of DOI:10.1002/zaac.200600227

The first representatives of a novel type of cyclic bisphosphines, namely, 1-aza-3,7-diphosphacyclooctanes (4, 5), were synthesized by condensation of 1,3-bis(arylphosphino)propanes (2, 3; aryl = phenyl or mesityl), formaldehyde and 5-aminoisophthalic acid. Only the meso isomers were obtained, in good to satisfactory yield. The cyclic bis-phosphines readily form P,P chelate complexes (6, 7) with [PtCl₂(cod)] (cod = 1,5-cyclooctadiene). The bisphosphine 4 and the corresponding complex 6 are soluble in water in the presence of two equivalents of alkali metal hydroxide. The molecular structures of 1-(meta-dicarboxyphenyl)-3,7-dimesityl-1-aza-3,7-diphosphacyclooctanes (5) and cis-{P,P-1-(meto-dicarboxyphenyl)-3,7-diphenyl-1-aza-3,7- diphosphacyclooctane}dichloroplatinum(II) (6) are reported.

Full text of DOI:10.1002/zaac.200600227

Articles
DOI: 10.1002/zaac.200600227
Synthesis, Molecular Structure and Coordination Chemistry of the First
1-Aza-3,7-diphosphacyclooctanes
Andrey A. Karasika,*, Roman N. Naumova, Yulia S. Spiridonovaa, Oleg G. Sinyashina, Peter Lönneckeb,
and Evamarie Hey-Hawkinsb,*
a Kazan/Russian Federation, A. E. Arbuzov Institute of Organic and Physical Chemistry
b Leipzig/Germany, Institut für Anorganische Chemie der Universität
Received August 3rd, 2006.
Abstract. The first representatives of a novel type of cyclic bis-
phosphines, namely, 1-aza-3,7-diphosphacyclooctanes (4, 5), were
synthesized by condensation of 1,3-bis(arylphosphino)propanes (2,
3; aryl ϭ phenyl or mesityl), formaldehyde and 5-aminoisophthalic
acid. Only the meso isomers were obtained, in good to satisfactory
yield. The cyclic bis-phosphines readily form P,P chelate complexes
(6, 7) with [PtCl2(cod)] (cod ϭ 1,5-cyclooctadiene). The bis-
phosphine 4 and the corresponding complex 6 are soluble in water
in the presence of two equivalents of alkali metal hydroxide. The
molecular structures of 1-(meta-dicarboxyphenyl)-3,7-dimesityl-1-
aza-3,7-diphosphacyclooctanes (5) and cis-{P,P-1-(meta-dicarboxy-
phenyl)-3,7-diphenyl-1-aza-3,7-diphosphacyclooctane}dichloro-
platinum(II) (6) are reported.
Keywords: P-ligands; 1,3-Bis(phenylphosphino)propane; 1,3-Bis-
(mesitylphosphino)propane;
Platinum
1-Aza-3,7-diphosphacyclooctanes;
Introduction
The preparation of cyclic bis-phosphines and their coordi-
nation chemistry are of great importance, because phos-
phines are excellent ligands for transition metals [1Ϫ4].
When the phosphorus atoms are incorporated into a ring
system, different coordination properties are observed in
comparison with non-cyclic analogues [1Ϫ3]. Among the
cyclic bis-phosphines, 1,5-diaza-3,7-diphosphacyclooctanes
are highly promising representatives. During the last decade
a
number of these heterocyclic bis-phosphines were
obtained via Mannich-type condensation of primary
phosphines, formaldehyde, and primary amines, including
compounds with chiral [5], unsaturated [6], ferrocenyl [7],
ferrocenylmethyl [8], o-oxyphenyl [9, 10], phosphinomethyl
[11] and amino acid [12, 13] substituents attached to the
heteroatoms of the 1,5-diaza-3,7-diphosphacyclooctane
ring system to give a number of asymmetric [5], polymetal-
lic [8], water-soluble [8Ϫ13] and chelate [5, 6, 8, 9, 12,
14Ϫ17] transition metal complexes.
However, their analogues in which a propylene chain
connects the two phosphorus atoms, the 1-aza-3,7-diphos-
phacyclooctanes, have not been described yet. Recently, we
have shown that instead of the desired eight-membered
* Prof. Dr. Andrey A. Karasik
Arbuzov str. 8
Kazan, 420088/Russian Federation
Fax: (007)8432732253
Tel: (007)8432732392
E-mail: karasik@iopc.knc.ru
* Prof. Dr. Evamarie Hey-Hawkins
Inst. für Anorg. Chemie der Universität
Johannisallee 29
D-04103 Leipzig
Fax: (0049)3419739319
Tel: (0049)3419736151
E-mail: hey@rz.uni-leipzig.de
Z. Anorg. Allg. Chem. 2007, 633, 205Ϫ210
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205

A. A. Karasik, R. N. Naumov, Yu. S. Spiridonova, O. G. Sinyashin, P. Lönnecke, E. Hey-Hawkins
heterocyclic 1-aza-3,7-diphosphacyclooctanes the unusual
macrocyclic 1,9-diaza-3,7,11,15-tetraphosphacyclohexa-
viously [24], and the procedure is similar to that employed
for water-soluble tertiary and secondary phosphines [25].
decane (1) is formed in the reaction of 1,3-bis(mesitylphos-
phino)propane with formaldehyde and benzylamine [18].
We have proposed that the relatively high basicity of ben-
zylamine is responsible for the self-assembly of the macro-
cycle.
We have previously shown that 5-aminoisophthalic acid,
in spite of the presence of two carboxyl groups, is still reac-
tive in Mannich-type condensation reactions giving rise to
water-soluble aminomethylphosphines [8, 19]. We now re-
port the synthesis and molecular structure of the first rep-
resentatives of a novel type of heterocyclic bis-phosphines,
namely, 1-aza-3,7-diphosphacyclooctanes, which are ob-
tained by condensation of 5-aminoisophthalic acid with
formaldehyde and bis(arylphosphino)propanes [aryl ϭ Ph
or 2,4,6-Me3C6H2 (Mes)] and the formation of the corre-
sponding chelate complexes with platinum(II).
In the 31P NMR spectra of 2 and 3 two signals were
observed, in accordance with the formation of the meso and
rac isomers in equal quantities.
There are some differences in the interaction of 2 and 3
with paraformaldehyde at 120 °C or formaldehyde (37 wt%
solution in water) in ethanol at room temperature. The bis-
phosphine 2 gives both isomers of bis[hydroxymethyl(phen-
yl)phosphino]propane (δ31P -21.0 and -21.3 ppm) in quanti-
tative yield as a viscous transparent liquid, while compound
3 gives a mixture of rac- and meso-bis[hydroxymethyl-
(mesityl)phosphino]propane (δ31P -26.8 and -27.0 ppm; up
to 75 %) and the monohydroxymethylated bis-phosphines
(δ31P -34.4 to -34.9 and -86.5 to -86.9 ppm).
The reaction of a diastereomeric mixture of rac- and
meso-1,3-bis(arylphosphino)propanes with formaldehyde
and 5-aminoisophthalic in boiling ethanol led, after cooling
of the reaction mixture, to the separation of the crystalline
meso isomers of the novel heterocyclic bis-phosphines 4 and
5 (eq. 2) instead of the 1,9-diaza-3,7,11,15-tetraphos-
phacyclohexadecanes. The crystalline products 4 and 5 were
obtained in 46 and 39 % yield.
Results and Discussion
1,3-Bis(phenylphosphino)propane (2) is a well-known com-
pound [20, 21], whereas we described 1,3-bis(mesitylphos-
phino)propane (3) only recently [18]. However, the reported
methods for the synthesis of secondary bis-phosphines have
some disadvantages. One method, in which lithium is used
to cleave tertiary bis-phosphines, takes rather long (up to
200 h) [21], but the reaction time could be decreased by em-
ploying ultrasonic irradiation [22]. Another inconvenient
route includes reduction of the corresponding bis-phosphi-
nates [23]. Finally, the deprotonation of a primary phos-
phine and subsequent alkylation of the corresponding alkali
metal phosphanide by organic dihalides is the most con-
venient way [20, 24], especially in the case of CsOH in DMF
as deprotonating agent [24]. To prepare the desired second-
ary bis-phosphines we utilized KOH in DMSO as depro-
tonating agent for the corresponding arylphosphines and
1,3-dibromo- or 1,3-dichloropropanes for the subsequent
alkylation reaction (eq. 1). The yields of the secondary bis-
phosphines 2, 3 are similar to the best results reported pre-
Bis-phosphines 4 and 5 are air-stable bright yellow com-
pounds. The chemical shifts in the 31P NMR spectra of
compounds 4 and 5 are shifted to lower field compared
with 1,3-diaza-3,7-diphosphacyclooctanes [5Ϫ9, 19] and de-
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First 1-Aza-3,7-diphosphacyclooctanes
1
The H NMR spectra of 4 and 5 are consistent with a
predominant crown conformation of the 1-aza-3,7-diphos-
phacyclooctanes with equatorial positions of the aryl
groups on the phosphorus atoms (orientation-dependent
2JPH in the P-CH2-N fragments) and are similar to those of
1,5-bis(3,5-dicarboxyphenyl)-3,7-diaryl-1,5-diaza-3,7-
diphosphacyclooctanes described recently [19]. In the 1H
and 13C NMR spectra of compound 5 very broad mul-
tiplets are observed for the AAЈXXЈ spin system, which
probably indicates restricted rotation of the bulky substitu-
ents around the exocyclic P-C bond.
Compound 4 is soluble in water in the presence of two
equivalents of sodium hydroxide. The NMR experiments
showed that no noticeable hydrolysis or oxidation of 4
occurred in water.
Fig. 1 ORTEP plot of the molecular structure of 5. H atoms and
DMF molecules are omitted for clarity.
The 31P NMR spectra of the reaction mixtures resemble
those observed for the macrocyclization yielding 1. Thus,
the spectrum of the reaction mixture of 1,3-bis(mesitylphos-
phino)propane (3), formaldehyde and 5-aminoisophthalic
acid after about 4 h of heating showed the presence of sec-
ondary phosphines (Ϫ86.4 to Ϫ86.9 ppm), different tertiary
aminomethylphosphines with cyclic oligomeric structures
(Ϫ32.9 to Ϫ33.4 and Ϫ36.2 to 37.5 ppm) and about 40 %
of the desired eight-membered ring 5. In the case of 4, a
small amount of crystals of 4 was formed right after the
start of the reaction in ethanol; therefore, no meaningful
NMR data of the reaction mixture could be obtained.
When the reaction was carried out in DMF, no solid
formed and the 31P NMR spectrum showed ca. 40 % of 4
and two groups of signals of other cyclic oligomers [Ϫ28.9
to Ϫ29.4 (30 %) and Ϫ32.6 to Ϫ33.4 ppm (30 %)]. Thus,
the reaction mixtures demonstrate the presence of intercon-
verting by-products, as was already observed in the forma-
tion of 1 [18].
Like 1,5-diaza-3,7-diphosphacyclooctanes [8, 14Ϫ17, 19],
the bis-phosphines 4 and 5 readily act as bidentate ligands
to form cis-chelate complexes (6 and 7) on reaction with
[PtCl2(cod)] (cod ϭ 1,5-cyclooctadiene, eq. 3).
The 31P NMR data for the platinum complexes 6 and 7
in DMSO and DMF (∆δ values (δcomplex-δligand) ca. 23 and
33 ppm with 1JPtP 3082 and 3039 Hz, respectively) are simi-
lar to those reported previously for related complexes with
1,5-diaza-3,7-diphosphacyclooctanes (∆δ ca. 40 to 45 and
1JPtP ca. 3050 Hz) [14Ϫ17, 19].
While the molecular structure of 6 (Fig. 2) is mainly as
expected for square-planar cis complexes with 1-aza-3,7-di-
phosphacyclooctanes [14], there are also some differences.
The heterocyclic ligand has a chair-boat conformation
with Pt-P-C(aryl) bond angles of ca. 118° and P-Pt-P bond
angles of ca. 84.5° (Table 2). The deviation of the Pt-P
bonds from the centroid of the three P-C bonds by about
6.5° indicates some distortion [14Ϫ17]. In 6, both phenyl
groups on the phosphorus atoms are eclipsed with one of
the neighbouring endocyclic P-C bonds of the propylene
bridge (torsion angles are 8.7° and 0.3°). The sterically
more demanding CH2N(aryl)CH2 fragment forms the boat
part of the heterocycle, resulting in an N1··Pt1 distance of
Table 1 Selected bond lengths /pm and angles /° for 5.
P(1)-C(14)
P(1)-C(2)
P(1)-C(1)
P(2)-C(23)
P(2)-C(4)
P(2)-C(5)
N(1)-C(5)
N(1)-C(1)
C(2)-C(3)
C(3)-C(4)
184.9(4)
185.1(4)
187.7(4)
185.8(4)
186.0(4)
187.4(4)
145.5(5)
145.6(4)
153.0(5)
154.4(5)
C(2)-P(1)-C(1)
C(4)-P(2)-C(5)
C(5)-N(1)-C(1)
N(1)-C(1)-P(1)
N(1)-C(5)-P(2)
N(1)-C(6)-C(7)
N(1)-C(6)-C(11)
C(3)-C(4)-P(2)
C(3)-C(2)-P(1)
C(2)-C(3)-C(4)
103.5(2)
104.6(2)
116.6(3)
112.4(2)
113.7(2)
121.1(3)
121.7(3)
115.4(3)
116.5(3)
114.8(3)
crease in this order with increasing steric hindrance of the
substituents at the phosphorus atom [19].
The X-ray analysis of 5 confirmed the proposed structure
(Fig. 1, Table 1). Only the isomer with axially orientated
lone pairs of electrons on the phosphorus atoms is present.
The heterocyclic molecules have a crown (chair-chair) con-
formation. The nitrogen atom is in an almost planar en-
vironment (the sum of the C-N-C bond angles is 358.4°)
and its hydrophilic substituent is in a pseudoaxial position.
The bulky aryl groups on the phosphorus atoms are per-
pendicular to the plane of the central eight-membered
ring to minimize steric hindrance, with the axial lone pairs
of electrons of both phosphorus atoms pointing in one
direction.
One of the included solvent molecules (DMF) forms hy-
drogen bonds to the carboxyl groups. Thus, no intermolecu-
lar hydrogen bonding is observed in 5 in spite of the pres-
ence of carboxyl groups, which are usually liable to forma-
tion of strong intermolecular hydrogen bonds [26Ϫ29].
In contrast to crystals of 5 obtained from DMF, solid
samples of 4 and 5 obtained from ethanol exhibit in their
IR spectra very broad ν(OH) bands centered near
2950 cmϪ1 with distinctive submaxima at ca. 2550 and
2650 cmϪ1 and ν(CϭO) at about 1690 cmϪ1 that can be
regarded as evidence for a very strong hydrogen bond [19]
of the type CϭO···HO(CϭO). Apparently, in the absence of
molecules of solvation a different type of molecular packing
results for 4 and 5 in which the carboxyl groups of neighb-
oring molecules exhibit strong intermolecular hydrogen
bonding.
Z. Anorg. Allg. Chem. 2007, 205Ϫ210
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207

A. A. Karasik, R. N. Naumov, Yu. S. Spiridonova, O. G. Sinyashin, P. Lönnecke, E. Hey-Hawkins
While the molecular structure of PtCl2 complexes of 1,5-
diaza-3,7-diphosphacyclooctanes and 1-aza-3,7-diphos-
phacyclooctanes are similar, the values of the stereospecific
coupling constant JPH for the protons of the P-CH2-N frag-
ment in 6 and 7 noticeably deviate from that of the corre-
sponding platinum complexes of 1,5-dicarboxyphenyl-3,7-
diaryl-1,5-diaza-3,7-diphosphacyclooctanes
[19].
This
deviation indicates some differences in the conformational
behaviour of 6 and 7 in comparison with the 1,5-diaza ana-
logues.
Due to the restricted rotation of the bulky mesityl groups
around the exocyclic P-C bonds the corresponding ortho-
methyl groups and meta-hydrogen atoms are inequivalent
1
in the H NMR spectra of 7.
Experimental Part
General Considerations
All manipulations were carried out with standard high-vacuum and
dry-nitrogen techniques. NMR spectra: Avance DRX 400 (Bruker),
standards: 1H NMR (400 MHz): internal solvent, 13C NMR
(100.6 MHz): internal solvent, 31P NMR (162 MHz): external 85 %
H3PO4. The IR spectra were recorded as KBr mulls on a Perkin-
Elmer FT-IR spectrometer System 2000 in the range 350-
4000 cmϪ1. The melting points were determined in sealed capillar-
ies and are uncorrected. PhPH2 [30], MesPH2 [31, 32] and
[PtCl2(cod)] [33, 34] were prepared according to literature pro-
cedures. Paraformaldehyde and 5-aminoisophthalic acid are com-
mercially available.
General procedure for the synthesis of 1,3-bis(phenyl-
phosphino)propane (2) and 1,3-bis(mesitylphos-
phino)propane (3)
0.17 mmol of freshly prepared KOH powder was added to a solu-
tion of 0.15 mmol of the corresponding primary phosphine in
200 mL of DMSO. In both cases the bright yellow reaction mixture
was stirred for 1 h. Then 0.08 mmol of 1,3-dibromo- or 1,3-di-
chloropropane in 50 mL of DMSO was added dropwise. The re-
sulting white suspension was stirred for 3 h, and then 150 mL of
water was added giving an exothermic reaction. The product was
extracted with 300 mL of n-hexane. The n-hexane solution was
dried 12 h with CaCl2. 1,3-Bis(phenylphosphino)propane (2) [20,
21] was isolated as a transparent liquid after distillation in 73 %
yield. B.p. 140 °C (0.2 mbar). 31P NMR (C6D6, δ in ppm, J in Hz):
Ϫ52.9 (1JPH 207), Ϫ54.0 (1JPH 207). 1,3-Bis(mesitylphosphino)pro-
pane (3) [18] was isolated as a white solid after evaporation of the
solvent in 90 % yield. M.p. 56-58 °C. 31P NMR (C6D6, δ in ppm,
J in Hz): Ϫ87.6 (1JPH 214), Ϫ87.8 (1JPH 214). The spectroscopic
data of 2 and 3 are in agreement with those reported previously.
Fig. 2 ORTEP plot of the molecular structure of compound 6. H
atoms (except OH) and DMSO molecules are omitted for clarity.
Table 2 Selected bond lengths /pm and angles /° for 6.
Pt(1)-P(2)
Pt(1)-P(1)
Pt(1)-Cl(2)
Pt(1)-Cl(1)
P(1)-C(6)
P(1)-C(5)
P(1)-C(1)
P(2)-C(3)
P(2)-C(20)
P(2)-C(2)
N(1)-C(1)
N(1)-C(2)
222.5(3)
223.2(3)
235.2(3)
236.2(3)
182(1)
182(1)
189(1)
182(1)
183(1)
188(1)
144(1)
147(1)
P(2)-Pt(1)-P(1)
P(2)-Pt(1)-Cl(2)
P(1)-Pt(1)-Cl(1)
Cl(2)-Pt(1)-Cl(1)
C(5)-P(1)-C(1)
C(6)-P(1)-Pt(1)
C(5)-P(1)-Pt(1)
C(20)-P(2)-Pt(1)
C(1)-N(1)-C(2)
N(1)-C(1)-P(1)
N(1)-C(2)-P(2)
C(3)-C(4)-C(5)
84.5(1)
92.9(1)
94.6(1)
87.8(1)
102.9(5)
118.1(4)
110.7(4)
118.3(4)
113.5(9)
113.7(7)
112.9(7)
118.2(9)
1-(meta-dicarboxyphenyl)-3,7-diphenyl-1-aza-3,7-
diphosphacyclooctanes (4)
˚
3.40 A. The nitrogen atom has a nearly trigonal-planar co-
ordination environment (sum of C-N-C bond angles is
355.4°). In summary, the structure of 6 is closely related to
that of the previously described PtCl2 complexes of 1,5-di-
aza-3,7-diphosphacyclooctanes [14Ϫ17].
A
solution of 1,3-bis(hydroxymethylphenylphosphino)propane
(2.54 g, 7.9 mmol), prepared in situ from bis(phenylphosphino)pro-
pane and paraformaldehyde, and 5-amino-isophthalic acid (1.44 g,
7.9 mmol) in 20 mL of ethanol was refluxed for 4 h. The resulting
yellow crystals were collected by filtration, washed with ethanol
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Z. Anorg. Allg. Chem. 2007, 205Ϫ210

First 1-Aza-3,7-diphosphacyclooctanes
(s, 1H, p-H in C6H3). 13C{1H} NMR (DMSO-d6, δ in ppm, J in Hz): 21.0 (s,
and dried in vacuum. Yield: 1.7 g, 46 %, m.p. (decomp.) 340-
346 °C. C25H25P2NO4 (465): C, 63.7 (calc. 64.5); H, 5.0 (5.4); N,
2.8 (3.0) %.
3
p-CH3 in Mes), 23.8 (m*, JCP 9.1, o-CH3 in Mes), 29.2 (s very br, PCH2),
2
30.2 (t br, JCP 27.3, CH2CH2P), 54.6 (m*, PCH2N), 117.5 (s, p-C in C6H3),
118.1 (s, o-C in C6H3), 129.8 (s, m-C in Mes), 131.8 (s, m-C in C6H3), 132.9
1
3
31P NMR (DMF-d7, δ in ppm): Ϫ31.5; (D2O ϩ 5 % NaOH, δ in ppm):
(d br, JCP 17.8, ipso-C in Mes), 138.9 (s, p-C in Mes), 144.0 (m*, JCP 8.3,
o-C in Mes), 146.9 (s, ipso-C in C6H3), 167.4 (s, CO2); * AAЈ part of an
AAЈXXЈ spin system. IR (cmϪ1, KBr): 1596, 1690 (CO and aryl), 2555,
2654 (OH).
Ϫ32.3. 1H NMR (DMF-d7, δ in ppm, J in Hz): 2.02 (m, 2H, CH2), 2.16-
2.41 (m, 4H, PCH2), 4.18 (dd, JHH 15.1, JPH 10.2, 2H, P-CH2BN), 4.28
2
2
(dd, JH3H 15.1, JPH 4.9, 2H, P-CH2AN), 7.43 (m, 6H, m-, p-H in C6H5),
7.69 (t, JHH 6.7, 4H, o-H in C6H5), 7.79 (s, 2H, o-H in C6H3), 8.02 c. (s,
1H, p-H in C6H3). 1H NMR (D2O ϩ 5 % NaOH, δ in ppm, J in Hz): 1.75-
2.15 (m, 6H, P(CH2)3P), 3.59 (s very br, 2H, P-CH2BN), 4.01 (s very br, 2H,
P-CH2AN), 7.31 (m, 6H, m-, p-H in C6H5), 7.40 (m, 4H, o-H C6H5), 7.49 (s,
2H, o-H in C6H3), 7.75 (s, 1H, p-H in C6H3). 13C{1H} NMR (DMF-d7, δ in
2
2
cis-{P,P-1-(meta-dicarboxyphenyl)-3,7-diphenyl-1-
aza-3,7-diphosphacyclooctane-κP, PЈ}dichloro-
platinum(II) (6)
1
ppm, J in Hz): 28.3 (d, JCP 16.5, PCH2), ca. 30 (obscured by DMF,
-CH2-CH2-), 58.9 (m, 1JCP 16.2, PCH2N), 118.0 (s br, p-, o-C in C6H3), 128.8
2
(s br, m-, p-C in C6H5), 132.1 (d, JCP 5.8, o-C in C6H5), 132.2 (s, m-C in
1
C6H3), 139.1 (d br, JCP 12.4, ipso-C in C6H5), 146.6 (s, ipso-C in C6H3),
A solution of 0.30 g (0.6 mmol) of 4 and 0.20 g (0.5 mmol) of
[PtCl2(cod)] in 15 mL of DMF was stirred for 1 d. The resulting
white crystals were collected by filtration and washed with ethanol.
Yield: 0.28 g, 70 %, m.p. > 360 °C. C25H25Cl2NO4P2Pt (731): C,
40.2 (calc. 41.0); H, 3.0 (3.4); N, 1.5 (1.9) %.
167.4 (s, CO2). IR (cmϪ1, KBr): 1596, 1691 (CO and aryl), 2550, 2652 (OH).
1-(meta-dicarboxyphenyl)-3,7-dimesityl-1-aza-3,7-
diphosphacyclooctane (5)
31P NMR (DMSO-d6, δ in ppm, J in Hz): Ϫ8.8 (1JPtP 3082); 1H NMR
(DMSO-d6, δ in ppm, J in Hz): 2.20-2.26 (m, 2H, CH2), 2.48-2.51 (m, P-
A solution of 1,3-bis(mesitylphosphino)propane (0.92 g, 2.7 mmol)
and 1 mL of formaldehyde (37 wt.% solution in water) in 10 mL of
ethanol was stirred overnight.
2
CH2, obscured by DMSO), 4.34 (br d, JHH 15.2, 2H, P-CHA2-N), 5.53 (d,
2JHH 15.2, 2H, P-CHB2-N), 7.53 (m, 4H, p-H in Ph and o-H in C6H3), 7.79
(s, 4H, o-H in Ph), 7.94 (s, 4H, m-H in Ph), 8.03 (s, p-H in C6H3).
Alternative procedure: 1,3-Bis(mesitylphosphino)propane (0.92 g,
2.7 mmol) and paraformaldehyde (0.35 g, 5.4 mmol) were heated at
120 °C for 2 h and the obtained mixture was dissolved in 10 mL
of ethanol.
cis-{P,P-1-(meta-dicarboxyphenyl)-3,7-dimesityl-1-
aza-3,7-diphosphacyclooctane-κP, PЈ}dichloro-
platinum(II) (7)
5-Aminoisophthalic acid (0.49 g, 2.7 mmol) in 10 mL of ethanol
was added to the obtained mixture of hydroxymethylphosphines.
The reaction mixture was refluxed for 10 h. Then the solvent was
reduced to half its volume under vacuum and 10 mL of acetone
was added to the reaction mixture. The resulting yellow crystals
were collected by filtration, washed with ethanol and dried in vac-
uum. Yield: 0.58 g, 39 %, m.p. 190-192 °C. C31H37P2NO4 (549): C,
67.2 (calc. 68.3); H, 6.2 (6.7); N, 2.3 (2.6) %.
A solution of 0.16 g (0.3 mmol) of 5 and 0.11 g (0.3 mmol) of
[PtCl2(cod)] in 10 ml of DMF was stirred for 1 d. The resulting
yellow crystals were collected by filtration. Yield: 0.15 g, 61 %, m.p.
> 360 °C. C31H37Cl2NO4P2Pt (815): C, 44.9 (calc. 45.6); H, 4.2
(4.5); N, 1.3 (1.7) %.
31P NMR (DMF-d7, δ in ppm, J in Hz): 1.0 (1JPtP 3039); 1H NMR (DMF-
d7, δ in ppm, J in Hz): 2.22-2.28 (m, 2H, CH2), 2.48-2.51 (m, 4H, P-CH2),
2.31 (s, 6H, p-CH3 in Mes), 2.56 (s, 6H, o-CH3 in Mes), 2.72 (s, 6H, o-CH3Ј
in Mes), 4.77 (br d, 2JHH 12.8, 2H, P-CHA2-N), 5.13 (br dd, 2JHH 12.8, 2JPH
12.3, 2H, P-CHB2-N), 6.93 (s, 2H, m-H in Mes), 7.02 (s, 2H, m-HЈ in Mes),
8.13 (s, 2H, o-H in C6H3) 8.26 (s, 1H, p-H in C6H3).
31P NMR (DMF-d7, δ in ppm): Ϫ32.2. 1H NMR (DMSO-d6, δ in ppm, J in
Hz): 1.84-1.89 (m, 4H, P(CH2)3P), 2.23 (s, 6H, p-CH3 in Mes), 2.47 (s, partly
obscured by DMSO, 12H, o-CH3 in Mes), ca. 2.50 (m, 2H, P(CH2)3P, ob-
scured by DMSO), 4.09 (d, JHH 14.4, 2H, P-CH2BN), 4.78 (d, JHH 14.4,
2
2
2H, P-CH2AN), 6.89 (s, 4H, m-H in Mes), 7.15 (s, 2H, o-H in C6H3), 7.79
Table 3 Crystal data and structure refinement for 5·3 DMF and 6·2 DMSO.
Empirical formula
Formula weight
Temperature
C40H58N4O7P2
768.84
208(2) K
C29H37Cl2NO6P2PtS2
887.65
213(2) K
Wavelength
71.073 pm
71.073 pm
Crystal system
Space group
Unit cell dimensions
monoclinic
P21/n
monoclinic
P21/c
a ϭ 1430.3(3) pm
b ϭ 1437.1(3) pm, β ϭ 98.475(4)°
c ϭ 2073.9(4) pm
4.2165(13) nm3
4
a ϭ 2267.4(4) pm
b ϭ 807.8(1) pm, β ϭ 112.794(4)°
c ϭ 2031.4(4) pm
3.4303(10) nm3
4
Volume
Z
Density (calculated)
Absorption coefficient
F(000)
1.211 Mg/m3
1.719 Mg/m3
0.154 mmϪ1
4.502 mmϪ1
1648
1760
Crystal size
0.20 ϫ 0.20 ϫ 0.20 mm
1.62 to 26.37°
24373
0.10 ϫ 0.10 ϫ 0.05 mm
1.95 to 26.36°
Θ range for data collection
Reflections collected
Independent reflections
Absorption correction
Refinement method
Data / restraints / parameters
Final R indices [I>2σ(I)]
R indices (all data)
19418
8599 [R(int) ϭ 0.0895]
SADABS
6981 [R(int) ϭ 0.0927]
SADABS
Full-matrix least-squares on F2
8599 / 25 / 524
R1 ϭ 0.0881, wR2 ϭ 0.1893
R1 ϭ 0.1402, wR2 ϭ 0.2116
Full-matrix least-squares on F2
6981 /25 / 387
R1 ϭ 0.0725, wR2 ϭ 0.1349
R1 ϭ 0.1182, wR2 ϭ 0.1537
Z. Anorg. Allg. Chem. 2007, 205Ϫ210
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
209

A. A. Karasik, R. N. Naumov, Yu. S. Spiridonova, O. G. Sinyashin, P. Lönnecke, E. Hey-Hawkins
[14] A. A. Karasik, A. V. Krashilina, A. T. Gubaidullin, I. A. Litvi-
X-ray analysis
nov, V. K.Cherkasov, O. G. Sinyashin, G. A. Abakumov, Russ.
The data were collected on a Siemens CCD diffractometer
(SMART) using Mo-Kα radiation (λ ϭ 71.073 pm) and ω-scan
rotation. Data reduction was performed with SAINT including the
program SADABS for empirical absorption correction. The struc-
ture was solved by direct methods and the refinement of all non-
hydrogen atoms was performed with SHELX97. H atoms were
mainly calculated on idealised positions. Structure figures were
generated with ORTEP [35]. CCDC 605905 (5) and CCDC
605904 (6) contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge
from the Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgments. Financial support from DFG-RFBR
(436RUS113/724/0-1 and 03-03-33085), DFG (No. 436 RUS 17/
60/01), and RFBR (No. 06-03-32754) is gratefully acknowledged.
A.A.K. thanks the Russian Science Support Foundation for a
research grant.
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210
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 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2007, 205Ϫ210