504
Note
Structural Characterization of N,N-
corresponding amine in the presence of the base tri-
ethylamine as the hydrogen chloride acceptor in one
step, cf. e. g. ref. [6], resulted in our hands often in
a mixture of compounds. To realize an efficient syn-
thesis according to Eq. 1, we divided the synthetic pro-
cedure in two steps.
Bis(diphenylphosphanyl)propylamine
Tobias Mayer and Hans-Christian Bo¨ttcher
Department Chemie, Ludwig-Maximilians-Universita¨t,
Butenandtstraße 5–13, D-81377 Mu¨nchen, Germany
NEt /CH Cl
2
Reprint requests to Prof. Dr. Hans-Christian Bo¨ttcher.
Fax: (+49) (0)89 / 2180 77407.
3
2
2Ph2PCl+ H2NnPr
→
Ph2PN(nPr)PPh2 (1)
−2NEt HCl
3
At first equimolar amounts of the amine and the
chlorophosphane were reacted in dichloromethane at
room temperature. After about 30 min a second equiv-
alent of the chlorophosphane was added. This re-
sulted in a clean synthesis of the desired N-substituted
bis(diphenylphosphanyl)amine without side products.
After workup, compound 1 was isolated as color-
less crystals in yields of about 63%. This procedure
Z. Naturforsch. 2012, 67b, 504 – 506
DOI: 10.5560/ZNB.2012-0089
Received March 29, 2012
Dedicated to Professor Joachim Heinicke on the occasion
of his 65th birthday
The synthesis and structural characterization of the N-
substituted bis(diphenylphosphanyl)amine Ph2PN(R)PPh2
(R = n-propyl, 1) is reported. Single crystals of 1 grown was also used in the preparation of some other N,N-
from dichloromethane/acetonitrile have been analyzed by X-
bis(diphenylphosphanyl)amines affording these com-
ray crystallography. The crystallographic study revealed that
pounds in similar yields [1]. The title compound 1
the diphenylphosphanyl groups in 1 are staggered relative
was characterized by elemental analysis, NMR spec-
to the PNP backbone as observed for other closely related
troscopy (1H, 13C, and 31P; see Experimental Section),
molecules.
and single-crystal X-ray diffraction.
Key words: Phosphorus, Organophosphorus Ligands,
Crystals of 1 belong to the monoclinic space group
Diphosphanes, N-Substituted
P21/c with four molecules in the unit cell. A se-
lected view of the molecule is shown in Fig. 1, appro-
priate bond lengths and angles are given in the cap-
tion. The molecular structure of 1 is comparable to
those of the reported ones of the type Ph2PN(R)PPh2
(R = benzyl [6], R = 1,2-dimethylpropyl [7]). As
found for the latter compounds, the diphenylphos-
phanyl groups are staggered relative to the PNP back-
bone. The angles around the central nitrogen atom
(see caption of Fig. 1) are comparable e. g. with
those in N,N-bis(diphenylphosphanyl)benzylamine:
P1−N1−P2, 120.6(1), P2−N1−C25, 120.8(2) and
P1−N1−C25, 113.3(2)◦ [6]. These structural param-
eters indicate that the phosphorus atoms exhibit a dis-
torted trigonal-pyramidal geometry, whereas the nitro-
gen atom in 1 is surrounded in a nearly trigonal-planar
array by the carbon and the two phosphorus atoms.
In the literature, the N,N-bis(diphenylphospha-
nyl)propylamine unit was characterized by X-ray
crystallography as the ligand in the complex
[ReBr(CO)3{Ph2PN(nPr)PPh2}] [9]. The bonding
Bis(phosphanyl)amines, X-Ray Diffraction
Introduction
Recently we reported some new coordinatively
unsaturated diruthenium complexes of the general
formula [ Ru2(CO)4(µ-H)(µ-PtBu2)(µ-PˆP)] (PˆP =
diphosphanes and N-substituted bis(diphenylphospha-
nyl)amines) [1]. These compounds represent good can-
didates for the synthesis of some new complexes bear-
ing trans-hyponitrito ligands [2]. During these studies
we used among others the N-substituted bis(diphenyl-
phosphanyl)amine Ph2PN(R)PPh2 (R = n-propyl, 1) as
the bridging ligand in the diruthenium metal core. The
syntheses of amino compounds of the latter type have
been described in the literature [3 – 6], however there
was no crystal structure report of the title compound
till now. In this paper we describe some modifications
in the synthesis of compound 1 as well as the result of
its characterization by X-ray crystallography.
Results and Discussion
We found that the reaction of two equivalents of characteristics of the latter agree well with the corre-
chlorodiphenylphosphane with one equivalent of the sponding ones of compound 1. Thus in the rhenium
c
Unauthenticated
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