Alternating stereoselective self-assembly of SSSS/RRRR or RSSR isomers of tetrakisphosphines in the row of 14-, 16-, 18- and 20-membered macrocycles

Article abstract of DOI:10.1039/c4dt01619j

Novel 18- and 20-membered P,N-macrocycles have been obtained stereoselectively by covalent self-assembly of α,ω-bisphosphines, formaldehyde and benzylamine. Alternating SSSS/RRRR or RSSR diastereomers were formed in the row of the 14-, 16-, 18- and 20-mem

Full text of DOI:10.1039/c4dt01619j

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Alternating stereoselective self-assembly of
SSSS/RRRR or RSSR isomers of tetrakisphosphines
in the row of 14-, 16-, 18- and 20-membered
macrocycles†
Cite this: Dalton Trans., 2014, 43,
12784
Roman N. Naumov,a Elvira I. Musina,*a Kirill B. Kanunnikov,a Tatiana I. Fesenko,a
Dmitry B. Krivolapov,a Igor A. Litvinov,a Peter Lönnecke,b Evamarie Hey-Hawkins,b
Andrey A. Karasika and Oleg G. Sinyashina
Novel 18- and 20-membered P,N-macrocycles have been obtained stereoselectively by covalent self-
assembly of α,ω-bisphosphines, formaldehyde and benzylamine. Alternating SSSS/RRRR or RSSR
diastereomers were formed in the row of the 14-, 16-, 18- and 20-membered macrocyclic aminomethyl-
phosphines. For the first time it was demonstrated that the stereochemical result of the reaction depends
on the even or odd number of the methylene groups between the two chiral phosphorus atoms in the
initial α,ω-bisphosphines.
Received 2nd June 2014,
Accepted 24th June 2014
DOI: 10.1039/c4dt01619j
www.rsc.org/dalton
Together with their apparent advantages these approaches
have drawbacks that hamper their wide application. Due to the
Introduction
Unlike macrocyclic amines, macrocyclic polyphosphines exist high stability of a M–P bond and the macrocyclic effect, the
as mixtures of diastereomers1 due to the higher inversion final demetallation step in template synthesis is rather
barrier of phosphines with an sp3-hybridized phosphorus difficult to achieve. The second approach is limited by deriva-
atom (150 kJ mol−1) compared to amines (30 kJ mol−1).2 Separ- tives of phosphole and phosphinine. We have proposed a
ation of these mixtures and isolation of individual isomers in novel solution for the problem concerning stereoselective syn-
a pure state are serious obstacles for the use of macrocyclic thesis of macrocyclic polyphosphines. This original method is
phosphines in coordination and supramolecular chemistry, as based on the covalent self-assembly in Mannich-type conden-
well as in catalysis. Two approaches that allow overcoming the sation reactions of 1,3-bis(arylphosphino)propanes, primary
problem have been developed.3 In a template synthesis, the alkylamines, and formaldehyde.1a,4 The self-assembly process
central metal ion is coordinated by the phosphorus donor in its classical conception is driven by lability of non-covalent
centers of an appropriate macrocyclic ligand in the most steri- forces or coordination bonds which are equally capable to be
cally favorable mode. Decomplexation yields a single diastereo- formed and dissociate in the course of reaction.5 It results in
mer, in which the directions of the lone pairs of electrons at reversibility of all steps of the reaction and its error correction
phosphorus replicate the direction of the coordinative bonds when thermodynamically less favorable intermediates, being
in the complex.1a,g The relatively low inversion barrier at phos- connected through the chain of reversible interactions, are
phorus in phospholes (approximately 67 kJ mol−1) and the able to be transformed into a single product with a higher
impossibility of inversion of an sp2-hybridized phosphorus thermodynamic stability. However, in some cases equilibrium
atom in phosphinines are applied in the second approach between interconnected intermediates, existing under self-
which facilitates the utilization of polyphospha-macrocycles.1a,g assembly conditions, may be affected by kinetics rather than
thermodynamic control, which shifts a reaction towards a
product with lower solubility.5 Unlike non-covalent linkages,
the number of examples in which covalent bonding is involved
in thermodynamically controlled self-assembly is relatively
limited.6 This limitation is mainly caused by the ability of only
certain types of covalent bonds to dissociate and to be formed
reversibly so that the equilibrium between all intermediates in
a reaction mixture would be under thermodynamic control.6
Among such bonds there are imine, amide, disulfide, disele-
aA.E. Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of
Sciences, Kazan Scientific Center, Arbuzov str. 8, Kazan, Russian Federation, 420088.
E-mail: elli@iopc.ru; Fax: +(007)8432732253; Tel: +(007)8432734893
bInstitut für Anorganische Chemie der Universität Leipzig, Johannisallee 29, D-04103
Leipzig, Germany. E-mail: hey@uni-leipzig.de; Fax: +(0049)3419739319;
Tel: +(0049)3419736151
†CCDC 973340 974210. For crystallographic data in CIF or other electronic
format see DOI: 10.1039/c4dt01619j
12784 | Dalton Trans., 2014, 43, 12784–12789
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nide, alkene, as well as carboxylate, organophosphorus and assigned to intermediate acyclic aminomethylphosphine pro-
borate ester bonds.4
ducts and several intensive signals in the narrow range −40 to
In 2004, the first stereoselective self-assembly of the −44 ppm. It should be underlined that in both cases one of
RPSPSPRP stereoisomer of the 16-membered macrocyclic ami- these signals essentially prevailed and corresponded to the
nomethylphosphine, namely 1,9-dibenzyl-3,7,11,15-tetramesi- stereoisomer of macrocyclic tetraphosphine which was isolated
tyl-1,9-diaza-3,7,11,15-tetraphosphacyclohexadecane,
was by the spontaneous crystallization from the reaction mixture.
described.7a Later, other 16-membered macrocyclic amino- Other close signals probably corresponded to other stereo-
methylphosphines (1) were reported: 1,9-diaza-3,7,11,15-tetra- isomers of the formed macrocycles.
phosphacyclohexadecanes with aryl (phenyl and mesityl)
As a result, the 18-membered 1,10-dibenzyl-3,8,12,17-tetra-
substituents on phosphorus atoms and various substituents mesityl-1,10-diaza-3,8,12,17-tetraphosphacyclooctadecane (5)
on nitrogen atoms (phenethyl, picolyl-2, picolyl-3, picolyl-4 and 20-membered 1,11-dibenzyl-3,9,13,19-tetramesityl-1,11-
and etc.).7b,c The stereoselective formation of only the RPSPSPRP diaza-3,9,13,19-tetraphosphacycloeicosane (6) were isolated as
stereoisomers was observed. The RPSPSPRP stereoisomers crystalline solids in moderate yield and were fully character-
1
of 1,9-diaza-3,7,11,15-tetraphosphacyclohexadecanes were ized by ESI-MS, H, 13C, 31P NMR spectroscopy, elemental and
obtained in good yields despite the fact that the starting X-ray diffraction studies (Scheme 2).
material, 1,3-bis(arylphosphino)propanes, was used as equi-
Only one set of signals corresponding to a single diastereo-
molar diastereomeric mixtures of meso and rac isomers. The mer was observed in the NMR spectra of the 18- and 20-mem-
reaction could have potentially resulted in five macrocyclic bered corands 5 and 6 proving the isolation of only one isomer
isomers. Moreover, in spite of the presence of six asymmetric of the macrocycles. It has been shown earlier that unlike the
atoms, chiral derivatives of 1,9-di-(R)- or -(S)-α-methylbenzyl- acyclic diphosphines the NMR spectra of the diastereomers of
3,7,11,15-tetramesityl-1,9-diaza-3,7,11,15-tetraphosphacyclo- the cyclic polyphosphines have a significant difference.10
1
hexadecanes were obtained as single diastereomers.7d
Additionally, the NMR H spectra of macrocyclic phosphines 5
The first example of covalent self-assembly of the 14-mem- and 6 had the characteristic features observed earlier for the
bered 1,8-diisopropyl-3,6,10,13-tetraphenyl-1,8-diaza-3,6,10,13- wide row of 16-membered macrocycles, namely 1,9-diaza-
tetraphosphacyclotetradecane (2) has been reported recently.8 3,7,11,15-tetraphosphacyclohexadecanes.7 For instance,
Unlike the 16-membered heterocycles, only the SPSPSPSP/ –PCH2N– group is observed in the H NMR spectra of 5 and 6
RPRPRPRP isomer of the 14-membered heterocycle was as an AMX spin system with one proton signal shifted upfield
a
1
obtained.
(δ = 2.63 (5) and 2.71 (6) ppm) in comparison with signals of
In order to find the dependence of stereoselectivity on the the corresponding protons for seven- and eight-membered
length of the chain between the phosphorus atoms we have cyclic aminomethylphosphines (3.2–3.6 ppm).7,11 The geminal
extended the borders of the ring sizes.
methylene protons of the benzyl fragment are nonequivalent
and observed as the AB spin system.
It should be mentioned that after few hours in the NMR
spectra of (5) and (6) appeared low intensive additional signals
at −40 to −44 ppm which might potentially be attributed to
Results and discussion
Two novel bis(arylphosphino)alkanes, namely 1,4-bis(mesityl- other diastereomers indeed detectable in 31P{1H} spectra.
phosphino)butane (3) and 1,5-bis(mesitylphosphino)pentane Afterwards the spectra did not change perhaps due to the equi-
(4), with longer aliphatic spacers between two asymmetric sec- librium establishing. It should be emphasized that the inter-
ondary phosphine groups, were synthesized in good yields. conversion of macrocyclic stereoisomers in solution confirms
Similar to 1,4-bis(phenylphosphino)butane and 1,5-bis(phe- the lability of the covalent bonds in the –PCH2N– fragment
nylphosphino)pentane that exist as a 1 : 1 mixture of diastereo- that provide the self-assembly of macrocycles in the Mannich-
mers,9 the rac and meso isomers of bisphosphines 3 and 4 type reaction. Recently we described the similar stereoisomer
have shown almost no difference in their NMR spectra. Only in interconversion for 7-membered 1-aza-3,6-diphosphacyclohep-
the 31P{1H} spectrum of 4 two close signals were observed tanes.11b,c
(Δδ = 0.03 ppm) that can be attributed to two diastereomers.
X-ray diffraction studies of the isolated products indicated
The one-pot condensation reaction of bis(mesitylphos- that the SPSPSPSP/RPRPRPRP isomer of the 18-membered corand
phino)alkanes 3 and 4 with benzylamine and formaldehyde 5 and the RPSPSPRP isomer of the 20-membered corand 6 were
was carried out for 28 hours at 80 °C with concentrations of formed in the course of the reaction (Fig. 1). It should be men-
reagents in the range of 0.1–0.3 M and without templating tioned that pounding and further drying of the macrocrystal-
reagents. The NMR monitoring of the reaction mixtures line products lead to substances with NMR data identical
showed that the reactions proceeded with the formation of to (5) and (6).
plenty of intermediates and the reaction mixtures were
X-ray diffraction studies showed that the two enantiomers
enriched by the isolated products only at the final stage, as in of product 5, being arranged as separate columns, form a true
the case of macrocyclizations described earlier for similar 16- racemic mixture (Fig. 2).
membered macrocycles.7 In the spectra of final reaction mix-
The X-ray data of the synthesized products demonstrate
tures there were minor signals at −28 to −32 ppm which were identity of the conformations found for the 14-membered
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In all the observed conformations there are two “genuine
corners” that are composed of an anti–gauche–gauche–anti
bond sequence with the same sign of torsion angles and two
“pseudocorners” in which the signs of torsion angles are oppo-
site (Fig. 3 and 4).
The numbers in square brackets indicate the number of
bonds between two “genuine” corners. In spite of the fact that
forcefield calculations demonstrated that the biangular [77]
conformation of 1,4,8,11-tetraoxacyclotetradecane is more
thermodynamically stable than the diamond-lattice quadran-
gular [3434] conformation,13 only a few examples of macro-
cycles existing in this conformation have been reported up to
now.14 The major difference between the biangular [77] and
[99] conformations that were found for the SPSPSPSP/RPRPRPRP
isomers with respect to biangular [88] and [1010] confor-
mations observed for the RPSPSPRP forms is that the former
possess C2 symmetry whereas the latter have a center of inver-
sion. In the biangular [77] and [99] conformations, one half of
a macrocycle, –CH2P(CH2)nPCH2N–, is the rotated analogue (by
2π/2 radians) of the other with the same configurations at the
asymmetric phosphorus atoms (SSSS or RRRR) and opposing
orientations of their lone pairs of electrons relative to each
other. In the biangular [77] and [99] conformations, the substi-
tuents at the nitrogen atoms are located on one side of the
macrocyclic plane. In contrast to the SPSPSPSP/RPRPRPRP forms,
each of two identical fragments –CH2P(CH2)nPCH2N– in the
[88] and [1010] conformations of the RPSPSPRP isomers is
related to the other half by an S2 symmetry operation. The two
phosphorus atoms in each half have different configurations
(RS), and the substituents at the amine units are located on
opposite sides of the plane of a macrocycle.
Fig. 1 Molecular structures of macrocycles 5 and 6 in ORTEP view
(only the ipso-C atoms of the mesityl groups at phosphorus atoms are
shown).
Fig. 2 Packing diagram of macrocycle 5. The molecules are oriented in
an “up-down” fashion.
macrocycles 2 and 5 on the one hand, and the 16-membered
derivatives 1 and 6 on the other hand. According to Dale’s
nomenclature,12 in which the torsion-angle sequences
between anti and gauche endocyclic bonds were assumed as a
basis, the conformations that were found in the solid state of
the P,N-containing corands could be designated as the non-
diamond lattice biangular [77] (14-membered aminomethyl-
phosphine 2),8 [88] (16-membered aminomethylphosphine 1),7
[99] (5), and [1010] (6) (Fig. 3 and 4).
The total number of possible diastereomers for 1,2,5,6 is
five: two rac forms existing as a pair of enantiomers (II and III,
Scheme 3) and three meso forms (I, IV, V, Scheme 3).
However, only the stereoisomer with SSSS/RRRR configur-
ation at phosphorus (type II) in the 14- and 18-membered
macrocycles 2 and 5 and the RSSR configuration (type I) in the
16- and 20-membered derivatives 1 and 6 was isolated stereo-
selectively (Schemes 1 and 2).
Thus, the configuration at phosphorus in the compounds
studied seems to obey a rule: if the two chiral phosphorus
centers in the macrocycle are linked by an odd number of
Fig. 3 Dale’s wedge representation of the [77] and [99] conformations
of the 14- and 18-membered macrocyclic aminomethylphosphines
(angles are given in degrees, °).
Fig. 4 Dale’s wedge representation of the [88] and [1010] confor-
mations of the 16- and 20-membered macrocyclic aminomethylphos-
phines (angles are given in degrees, °).
Scheme 1 14- and 16-membered P,N-macrocycles.
12786 | Dalton Trans., 2014, 43, 12784–12789
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Synthesis of 1,4-bis(mesitylphosphino)butane (3) and 1,5-
bis(mesitylphosphino)pentane (4). 1,4-Bis(mesitylphosphino)-
butane and 1,5-bis(mesitylphosphino)pentane were syn-
thesized similarly to the method applied earlier for the prepa-
ration of 1,3-bis(mesitylphosphino)propane.11a
0.23 mmol of freshly prepared KOH powder was suspended
in 50 mL DMSO and added to a solution of 0.12 mmol of mesi-
tylphosphine in 50 mL DMSO. The yellow reaction mixture was
stirred for 1 h. Then 0.06 mmol of the corresponding
1,4-dibromobutane or 1,5-dibromopentane in 50 mL of DMSO
was added dropwise. The resulting white suspension was
stirred for 5 h, and then 100 mL of degassed water was added
giving an exothermic reaction. The product was extracted with
three 100 mL portion of n-hexane. The n-hexane solution was
dried for 12 h over CaCl2.1,4-Bis(mesitylphosphino)butane (3)
and 1,5-bis(mesitylphosphino)pentane (4) were isolated as a
white solid after evaporation of the solvent.
Scheme 2 Mannich-type condensation reaction of bis(mesitylphos-
phino)alkanes, primary amines and formaldehyde.
1,4-Bis(mesitylphosphino)butane (3). Yield: 16.3 g, 76%,
mp 56–58 °C. 31P NMR (CDCl3, ppm): −87.3 (d, 1JPH 217.1 Hz).
1H NMR (CDCl3, ppm): 1.47 (4H, br. m, PCH2CH2), 1.55 (2H,
br. m, PCH2), 1.72 (2H, br. m, PCH2), 2.25 (6H, s, p-CH3 in
Scheme 3 Possible diastereomers of macrocyclic tetrakisphosphines
1,2,5,6.
1
methylene groups, the RPSPSPRP (type I) stereoisomer is
adopted. If the phosphorus atoms in the macrocycle are linked
by an aliphatic chain consisting of an even number of methy-
lene groups, the SPSPSPSP/RPRPRPRP (type II) isomer is formed.
Mes), 2.43 (12H, s, o-CH3 in Mes), 4.21 (2H, br. d, JHP
217.1 Hz, P-H), 6.87 (4H, s, m-H in Mes). 13C{1H} NMR (CDCl3,
1
ppm): 21.09 (s, p-CH3 in Mes), 21.25 (d, JCP 12.0 Hz, PCH2),
3
2
3
23.15 (d, JCP 11.1 Hz, o-CH3 in Mes), 30.17 (t, JCP ≈ JCP 8.5
3
Hz, PCH2CH2), 128.99 (d, JCP 2.9 Hz, m-C in Mes), 130.26
1
(d, JCP 14.0 Hz, ipso-C in Mes), 137.98 (s, p-C in Mes), 141.82
(d, 2JCP 11.6 Hz, o-C in Mes).
Conclusions
1,5-Bis(mesitylphosphino)pentane (4). Yield: 18.3 g, 82%,
mp 59–61 °C. 31P{1H} NMR (CDCl3, ppm): −86.9, −86.8. 31P
In conclusion, we have demonstrated the effectiveness of the
covalent self-assembly approach for the stereoselective syn-
thesis of SPSPSPSP/RPRPRPRP or RPSPSPRP stereoisomers of
18- and 20-membered macrocyclic tetrakisphosphines. It is
established that the even or odd number of methylene groups
between two chiral phosphorus atoms favors the selection of
relative configuration of phosphorus atoms (SSSS/RRRR or
RSSR respectively) in the row of 14-, 16-, 18-, and 20-membered
aminomethylphosphine corands.
1
1
NMR (CDCl3, ppm): −86.8 (d, JPH 217.6 Hz). H NMR (CDCl3,
ppm): 1.40 (6H, br. m, PCH2(CH2)3CH2P), 1.55 (2H br. m,
PCH2), 1.74 (2H, br. m, PCH2), 2.26 (6H, s, p-CH3 in Mes), 2.45
(12H, s, o-CH3 in Mes), 4.22 (2H, dt, 1JHP 217.6 Hz, 3JHP 6.7 Hz,
P-H), 6.89 (4H, s, m-H in Mes). 13C{1H} NMR (CDCl3, ppm):
21.11 (s, p-CH3 in Mes), 21.51 (d, 1JCP 11.6 Hz, PCH2), 23.17 (d,
2
3JPC 11.2 Hz, o-CH3 in Mes), 28.48 (d, JCP 8.3 Hz, PCH2CH2),
3
3
32.36 (t, JCP 8.5 Hz, PCH2CH2CH2CH2CH2P), 129.03 (d, JCP
1
2.9 Hz, m-C in Mes), 130.45 (d, JCP 14.9 Hz, ipso-C in Mes),
137.97 (s, p-C in Mes), 141.86 (d, 2JCP 11.5 Hz, o-C in Mes).
(RRRR/SSSS)-1,10-Dibenzyl-3,8,12,17-tetramesityl-1,10-diaza-
3,8,12,17-tetraphosphacyclooctadecane (5). A solution of 1,4-
bis(mesitylphosphino)butane (3) (0.33 g, 0.9 mmol) and para-
formaldehyde (0.06 g, 2.0 mmol) in DMF (5 mL) was stirred for
Experimental
General procedures
All manipulations were carried out with standard high-vacuum 2 hours at 80 °C. Then a solution of benzylamine (0.11 g,
and dry-nitrogen techniques. Solvents were dried and degassed 1.0 mmol) in DMF (5 mL) was added dropwise for 3 hours at
prior to use and stored under a nitrogen atmosphere. The 80 °C. After the reaction mixture was cooled to room tempera-
NMR experiments were performed on an Avance 600 (Bruker) ture, the formation of a crystalline product was observed after
spectrometer, standards: 31P NMR (242.97 MHz): external 85% 24 hours. The white crystals were filtered off, the crystals suit-
H3PO4; 1H NMR (600.13 MHz): internal solvent; 13C NMR able for X-ray diffraction were hand picked and then the pre-
(150.90 MHz): internal solvent; Avance DRX 400 (Bruker) cipitate was washed with DMF and dried under reduced
1
spectrometer, standards: H NMR (400 MHz): internal solvent; pressure. Yield: 0.21 g, 47%, mp 183–185 °C. 31P{1H} NMR,
13C NMR (100.6 MHz): internal solvent; 31P NMR (162 MHz): (CDCl3, ppm): −41.6. 1H NMR (CDCl3, ppm): 1.49–1.67 (8H,
external 85% H3PO4. The ESI mass spectra were obtained on a br. m, PCH2CH2), 1.93–2.03 (8H, m, PCH2), 2.22 (12H, s, p-CH3
2
Bruker Esquire 3000 Plus. The melting points were determined in Mes), 2.45 (24H, s, o-CH3 in Mes), 2.63 (4H, dd, JHH 12.7
2
2
on Boetius apparatus and are uncorrected.
Hz, JHP 9.3 Hz, PCH2N), 3.16 (2H, d, JHH 12.7 Hz, CH2Ph),
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2
2
3.96 (4H, d, JHH 12.7 Hz, PCH2N), 4.42 (2H, d, JHH 12.7 Hz, grated, and scaled using the APEX2 data reduction package17
CH2Ph), 6.80 (8H, s, m-H in Mes), 7.21 (10H, m, Ph). 13C{1H} and corrected for absorption using SADABS.18 The structure
NMR (C6D6, ppm): 20.95 (s, p-CH3), 23.87 (d, JCP 19.0 Hz, was solved by direct methods using SHELX97. All non-hydro-
3
o-CH3), 26.33–27.02 (br. m, PCH2 overlapped with PCH2CH2), gen atoms were refined anisotropically. H atoms were calcu-
1
55.93 (d, JCP 8.7 Hz, PCH2N), 62.86 (br. m, CH2Ph), 127.14 (s, lated on idealized positions and refined as riding atoms.
p-C in Ph), 127.82–128.31 (o-C and m-C in Ph overlapped with Pictures were generated with ORTEP3 for Windows.19 CCDC
1
C6D6), 129.84 (br. d, JCP 28.0 Hz, ipso-C in Mes overlapped 973340 (5), 974210 (6) contain the supplementary crystallo-
with m-C in Mes), 130.02 (br. s, m-C in Mes overlapped with graphic data for this paper.
4
ipso-C in Mes), 138.80 (d, JCP 2.9 Hz, p-C in Mes), 140.33 (s,
2
Crystal data, structure refinement for compound 5
ipso-C in Ph), 144.87 (d, JCP 14.9 Hz, o-C in Mes). MS (ESI+)
m/z (%): 995 (20, [M + H + O]+), 1011 (60, [M + H + 2O]+), 1015
(100,[M + 2H2O]+), 1027 (33, [M + H + 3O]+), 1043 (19, [M + H +
4O]+). Anal. calc. for C62H82N2P4 [979]: C, 76.1; H, 8.4; N, 2.9;
P, 12.7. Found: C, 75.9; H, 8.4; N, 2.8; P, 12.6%.
C62H82P4N2 2 DMF (5); M = 1125.37, monoclinic, space group
C2/c, a = 32.657(1), b = 12.9533(4), c = 16.2958(5) Å, β =
105.974(3)°, V = 6627.1(4) Å3, Z = 4, Dcalc = 1.128 g cm−3; μ(Mo-
Kα) = 0.158 mm−1; 30 265 reflections measured, 4752 indepen-
dent reflections. Final R1 = 0.0532, Rw = 0.1195 for reflections
with I ≥ 2σ(I), and R1 = 0.1134, Rw = 0.1394 for all reflections.
(RSSR)-1,11-Dibenzyl-3,9,13,19-tetramesityl-1,11-diaza-3,9,13,19-
tetraphosphacycloeicosane (6). Compound 6 was synthesized
similar to 5 from 1,5-bis(mesitylphosphino)pentane (4) (0.35 g,
0.9 mmol). Yield: 0.27 g, 57%, mp 189–191 °C. 31P{1H} NMR, Crystal data, structure refinement for compound 6
1
(CDCl3, ppm): −42.0. H NMR (CDCl3, ppm): 1.48–1.58 (12H,
ˉ
C64H86P4N2 (6); M = 1007.22, triclinic, space group P1, a =
8.978(7), b = 11.999(9), c = 15.378(11) Å, α = 77.012(8), β =
86.156(9), γ = 70.547(8)°, V = 1522.2(19) Å3, Z = 1 (molecule is
located on a special position), Dcalc = 1.099 g cm−3; μ(Mo-Kα) =
0.162 mm−1; 11 374 reflections measured, 5840 independent
reflections. Final R1 = 0.0778, Rw = 0.2112 for reflections with
I ≥ 2σ(I), and R1 = 0.1370, Rw = 0.2573 for all reflections.
br. m, PCH2(CH2)3CH2P), 1.83 (4H, m, PCH2), 2.02 (4H, m,
PCH2), 2.24 (12H, s, p-CH3 in Mes), 2.46 (24H, s, o-CH3 in
2
2
Mes), 2.71 (4H, dd, JHH 12.7 Hz, JHP 7.2 Hz, PCH2N), 3.14
2
2
(2H, d, JHH 12.7 Hz, CH2Ph), 3.90 (4H, d, JHH 12.7 Hz,
PCH2N), 4.32 (2H, d, 2JHH 12.7 Hz, CH2Ph), 6.82 (8H, s, m-H in
Mes), 7.17–7.20 (10H, br. m, Ph). 13C{1H} NMR (C6D6, ppm):
20.95 (s, p-CH3), 23.87 (d, JCP 19.0 Hz, o-CH3), 27.32 (d, JCP
14.2 Hz, PCH2), 29.34 (d, 2JCP 24.0 Hz, PCH2CH2), 33.91 (t, 3JCP
3
1
1
14.3 Hz, PCH2CH2CH2CH2CH2P), 56.44 (d, JCP 10.0 Hz,
PCH2N), 61.44 (t, JCP 9.2 Hz, CH2Ph), 127.16 (s, p-C in Ph),
Acknowledgements
3
127.82–128.30 (m-C in Ph overlapped with C6D6), 129.74 (br. s,
o-C in Ph overlapped with C6D6), 130.02 (d, 3JCP 3.8 Hz, m-C in
Mes), 131.48 (br. d, JCP 20.5 Hz, ipso-C in Mes), 138.77 (s, p-C
This work was supported by RFBR (no.12-03-97083-r_povolz-
hye_a, 13-03-00563).
1
in Mes), 140.25 (s, ipso-C in Ph), 144.73 (d, 2JCP 14.7 Hz, o-C in
Mes). MS (ESI+) m/z: 1024 (24, [M + H + O]+), 1040 (24, [M + H
+ 2O]+), 1043 (44, [M + 2H2O]+), 1056 (20, [M + H + 3O]+), 1072
(100, [M + H + 4O]+), 1094 (68, [M + Na + 4O]+). Anal. calc. for
C64H86N2P4 [1007]: C, 76.3; H, 8.6; N, 2.8; P, 12.3. Found: C,
76.2; H, 8.5; N, 2.7; P, 12.2%.
Notes and references
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X-ray crystallography data
The crystals of 5 and 6 suitable for X-ray diffraction were hand
picked from precipitates that separated from the reaction mix-
tures. The data of 5 were collected on a Gemini diffractometer
(Agilent Technologies) using MoKα radiation (λ = 0.71073 Å)
and ω-scan rotation. Data reduction was performed with Crys-
Alis-Pro15 including the program SCALE3 ABSPACK for empiri-
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methods and the refinement of all non-hydrogen atoms was
performed with SHELX97.16 The molecule is located on a
special position (C2-axis) and mesityl substituents and solvent
molecules (DMF) were found to be disordered. All non-hydro-
gen atoms were refined anisotropically, H atoms were calcu-
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were collected on a Bruker Smart Apex II CCD diffractometer
using graphite monochromated MoKα (λ = 0.71073 Å) radiation
and ω-scan rotation. Data collection images were indexed, inte-
12788 | Dalton Trans., 2014, 43, 12784–12789
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