Novel heterocyclic P-ligands: Synthesis and application in Pt(II) complexes

Article abstract of DOI:10.1080/10426500701735544

3-Diphenylphosphino-1,2,3,6-tetrahydro- and 1,2,3,4,5,6-hexahydro- phosphinines, as well as dibenzo[c,e][1,2]oxaphosphorines (L) were prepared and used in the synthesis of the corresponding cis chelate Pt(II) complexes and PtCl2L2 complexes, respectively.

Full text of DOI:10.1080/10426500701735544

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Phosphorus, Sulfur, and Silicon
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Novel Heterocyclic P-Ligands:
Synthesis and Application in
Pt(II) Complexes
György Keglevich a , Andrea Kerényi a , Melinda Sipos
a , Annamária Balassa a & Tamás Körtvélyesi b
a Department of Organic Chemistry and Technology ,
Budapest University of Technology and Economics ,
Budapest, Hungary
b Department of Physical Chemistry , University of
Szeged , Szeged, Hungary
Published online: 20 Jun 2008.
To cite this article: György Keglevich , Andrea Kerényi , Melinda Sipos , Annamária
Balassa & Tamás Körtvélyesi (2008) Novel Heterocyclic P-Ligands: Synthesis and
Application in Pt(II) Complexes, Phosphorus, Sulfur, and Silicon and the Related
Elements, 183:2-3, 440-444, DOI: 10.1080/10426500701735544
To link to this article: http://dx.doi.org/10.1080/10426500701735544
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Phosphorus, Sulfur, and Silicon, 183:440–444, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701735544
Novel Heterocyclic P-Ligands: Synthesis and Application
in Pt(II) Complexes
1
1
1
¨
´
Gyorgy Keglevich, Andrea Kerenyi, Melinda Sipos,
1
2
´
´
¨
´
Annamaria Balassa, and Tamas Kortvelyesi
1Department of Organic Chemistry and Technology, Budapest
University of Technology and Economics, Budapest, Hungary
2Department of Physical Chemistry, University of Szeged, Szeged,
Hungary
3-Diphenylphosphino-1,2,3,6-tetrahydro- and 1,2,3,4,5,6-hexahydro-phosphinines,
as well as dibenzo[c,e][1,2]oxaphosphorines (L) were prepared and used in the
synthesis of the corresponding cis chelate Pt(II) complexes and PtCl L com-
2
2
plexes, respectively. The latter family of compounds includes 7-membered ring Pt(II)
complexes.
Keywords P-heterocycles; monodental and bidental P-ligands; Pt(II) complexes; ring
Pt(II) complexes; stereospecific 3J(P-Pt) NMR couplings
INTRODUCTION
In this article, we summarize our recent results on P-ligands and
their platinum complexes. It was found earlier that the interaction of
arylphospholes and dichlorodibenzonitrile platinum formed a mixture
of a monophosphole and a diphosphole complex, this latter with trans
orientation of the hetero rings.1 As a comparison, an analogous reaction
of the Mathey-phosphole led, almost exclusively, to the cis diphosphole
complex. The difference is due to the presence or lack of steric hin-
drance. Other P-heterocycles, such as phosphabicyclo[3.1.0]hexanes,
1,2-dihydrophosphinines and 1,4-dihydrophosphinines were converted
to Rh(III) or Pd(II) complexes.2
This project was supported by the European Union and the Hungarian State (GVOP-
3.2.2.-2004-07-0006/3.0) and jointly by the Hungarian Scientific Research Fund (OTKA,
Grant No. T067679).
Address correspondence to Gyo¨rgy Keglevich, Department of Organic Chemistry
and Technology, Budapest University of Technology and Economics, H-1521 Budapest,
Hungary. E-mail: keglevich@mail.bme.hu
440

Novel Heterocylic P-Ligands
441
New phosphinine derivatives with exocyclic P-functions were de-
veloped by us (Scheme 1). The Michael-addition of diphenylphos-
phine oxide to 1-phenyl-1,2-dihydrophosphinine oxide (1) afforded a 3-
diphenylphosphinoxido-1,2,3,6-tetrahydrophosphinine oxide (2)3 that
was converted to the corresponding 1,2,3,4,5,6-hexahydrophosphinine
oxide (3).4 Both bis(phosphine oxides) were formed in a diastere-
oselective manner, whose stereostructures were evaluated by DFT
calculations and/or stereospecific NMR couplings. The phosphinoxido-
tetrahydrophosphinine oxide (2) was subjected to double deoxygena-
tion to provide the corresponding bis(phosphine) with preserved
stereochemistry that on reaction with the platinum precursor led to a
cis chelate complex (4).5 The phosphinoxido-hexahydrophospinine ox-
ide (3) was taken in a similar sequence of reactions to furnish another
cis chelate complex (5) as the final outcome.6
SCHEME 1
On a related topic, dibenzo-oxaphosphorines with a variety of P-
substituents were synthesized and used in complexations. In the first
place, aryl-dibenzooxaphosporines (7) were made available from the P-
chloro derivative (6), and than converted to the platinum complexes
containing only one heterocyclic unit. It was interesting to find, on the
basis of stereospecific Pt–P couplings, that in the case of phenyl sub-
stituent a cis complex (8), while in the case of triisopropylphenyl group
a trans complex (9) was formed (Scheme 2).7
Then a few P-alkoxy and P-amino dibenzooxaphosphorines (10) were
prepared and transformed to the corresponding platinum complexes
(11) that in this particular case contained two heterocyclic P-ligands,
moreover in position cis.8 In the next stage, α-phenylethylamino- and
menthyl-dibenzooxaphosphorines (12 and 14)8 with optical activity and

442
G. Keglevich et al.
SCHEME 2
the related complexes (13 and 15)9 were synthesized (Scheme 3). In the
first case, the complex (11) was formed in a homo- and a heterochiral
form, while in the other two cases, the complexes (13 and 15) were
obtained in two homochiral forms and a heterochiral form.
SCHEME 3
The L-prolin methyl ester served as an additional reagent for the
P-substitution of the chloro-dibenzooxaphosphorine (6). Complexation
of the prolino-dibenzooxaphosphorine (16) led to the cis form of the
bis(dibenzooxaphosphorino) platinum complex (17) (Scheme 4).

Novel Heterocylic P-Ligands
443
SCHEME 4
Ring opening reaction accompanying the substitution of the start-
ing dibenzooxaphosphorine (6) furnished a new P-ligand (18), which
on reaction with the platinum precursor gave a bis(triarylphosphino)
complex (19) (Scheme 5). In this case, the substituents were, however,
in the trans disposition, as suggested by sterospecific Pt–P couplings.10
SCHEME 5
Phosphorylation of the 1-hydroxy-1ꢀ-diphenylphosphino-biphenyl
(18) with chloro-dibenzooxaphosphorine offered a newer possibility for
ligand modification. Complexation of the special bidentate P-ligand (20)
so obtained, led to a special ring Pt-complex (21) (Scheme 6).10
SCHEME 6
Aiming at the synthesis of further bidental P-ligands, methy-
laminoethanol was reacted with two equivalents of chloro-
dibenzooxaphosphorine (6). The reaction took place smoothly and
the resulting bisdibenzooxaphosphorine (22) was utilized in the
preparation of a ring platinum complex (23) (Scheme 7).
L-Ephedrine was taken in a similar sequence of reactions to afford,
eventually, an analogous 7-ring platinum complex (25) (Scheme 8).

444
G. Keglevich et al.
SCHEME 7
SCHEME 8
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