Synthesis of Binam-P Derived C2-Symmetric bis-Iminophosphonamide Ligands. Molecular Structure of [(R)-Binam(Ph2PN(H)tBu)2]

Article abstract of DOI:10.1002/zaac.201800508

The Staudinger reaction of organic azides tBuN₃, 1-Ad-N₃, and DippN₃ (Dipp = 2,6-diisopropylphenyl) with (R)-N,N′-bis(diphenylphosphanyl)-2,2′-diamino-1,1′-binaphthyl [(R)-Binam-P], obtained by an optimized procedure from (R)-(+)-Binam, Ph₂PCl, and Et₃N in DCM, leads to preparation of a series of new C₂-symmetric bis-iminophosphonamide ligands [(R)-Binam(Ph₂PN(H)R)₂] [R = tBu (1), Ad (2), and Dipp (3)]. The molecular structure of 1·2DMSO was confirmed by X-ray structure analysis.

Full text of DOI:10.1002/zaac.201800508

Journal of Inorganic and General Chemistry
DOI: 10.1002/zaac.201800508 SHORT COMMUNICATION
Zeitschrift für anorganische und allgemeine Chemie
Synthesis of Binam-P Derived C2-Symmetric
bis-Iminophosphonamide Ligands. Molecular Structure of
[(R)-Binam(Ph2PN(H)tBu)2]
Konstantin A. Rufanov,*[a] Ilya Yu. Titov,[b] Alex R. Petrov,[c] Klaus Harms,[c] and Jörg Sundermeyer[c]
Abstract. The Staudinger reaction of organic azides tBuN3, 1-Ad-N3,
DCM, leads to preparation of a series of new C2-symmetric bis-imino-
and DippN3 (Dipp = 2,6-diisopropylphenyl) with (R)-N,NЈ-bis(diphen- phosphonamide ligands [(R)-Binam(Ph2PN(H)R)2] [R = tBu (1), Ad
ylphosphanyl)-2,2Ј-diamino-1,1Ј-binaphthyl [(R)-Binam-P], obtained (2), and Dipp (3)]. The molecular structure of 1·2DMSO was con-
by an optimized procedure from (R)-(+)-Binam, Ph2PCl, and Et3N in firmed by X-ray structure analysis.
Iminophosphonamide anions [R2P(NRЈ)2]– (NPN) are isolo- mono-NPN scaffolds of the type A[5] and bifunctional imino-
bal analogues of phosphinate anions, in which oxygen atoms phosphoranes bearing a chiral pendant hydrogen bonding unit
are replaced by imido-groups. Synthesis of this NPN-ligand of the type B (Chart 2).[6]
family is known from the literature and it is based on two
The class of bis-iminophosphonamides has been presented
main protocols – the Staudinger reaction[1,2] of phosphorus(III) by two series of C2-symmetric molecules known so far. Earlier
compounds with organic azides and the Kirsanov condensa- Hill and co-workers introduced rac-DACH-bridged ligands
tion[3] of bromophosphonium bromides with primary amines (DACH = trans-1,2-diaminocyclohexane) (Chart 2, C).[7] Che-
in the presence of the auxiliary base and subsequent deproton- lating bis-NPN aluminum and rare-earth metal complexes with
ation (Chart 1).
these NPN-ligands showed high activity as a single-component
catalysts for the stereoselective polymerization of α-methyl-
methacrylate.
Next, one of us communicated two novel chiral superbases
with dimethylamino and pyrrolidino substituents each of two
P2-phosphazenyl groups linked via a C2-symmetric 1,1Ј-bi-
naphthyl-2,2Ј-diamine (Binam) backbone (Chart 2, D). Their
outstanding superbasicity leads to interesting perspectives for
application in asymmetric Brønsted base catalysis.[8]
Chart 1. Synthetic protocols to iminophosphonamide species.
Iminophosphonamides belong to the class of P1-phos-
phazenes, those chiral species are receiving increasing atten-
tion as superbase organocatalysts, performing a broad scope of
stereodifferentiating reactions.[4] Among them there are two
types that dominate to date as chiral catalysts – P-spirocyclic
* Dr. K. A. Rufanov
E-Mail: kruf@mail.ru
[a] Department of Chemistry
M.V. Lomonosov State University of Moscow
119991 Moscow, Russian Federation
[b] N.D. Zelinsky Institute of Organic Chemistry
Russian Academy of Sciences
Leninsky Pr., 47
Chart 2. Types of chiral superbases known to date.
119991 Moscow, Russian Federation
[c] Fachbereich Chemie der Philipps-Universität Marburg
Hans-Meerwein-Strasse 4
In the course of our systematic studies of ambidentate
organophosphorus(V) donor ligands of the general type
35032 Marburg, Germany
Z. Anorg. Allg. Chem. 0000, ᭿,0–0
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Journal of Inorganic and General Chemistry
SHORT COMMUNICATION
Zeitschrift für anorganische und allgemeine Chemie
[R2P(X)Z]– (X, Z = S, NRЈ, CH2, CHRЈ, Cp, Ind, Flu; as for
Thus obtained (R)-(+)-Binam-P was transformed by the
X = Z and X ϶ Z)[9] our attention has been drawn to the chem- Staudinger reaction with three different organic azides –
istry of this NPN-ligand family.
tBuN3, AdN3, and DippN3 (Ad = adamantyl-1, Dipp = 2,6-
Recently we reported[10] on the rare-earth metal chemistry diisopropylphenyl) into a series of sterically hindered bis-imi-
of highly basic, easily accessible, sterically demanding and nophosphonamides (NPN ligands): [(R)-Binam(Ph2PN(H)R)2]
perfectly soluble N,NЈ-bis(tert-butylimino)-phosphonamide [R = tBu (1), Ad (2), and Dipp (3)] (Scheme 1). In all three
(NPN) ligand Ph2P(=N–tBu)N(H)tBu and shortly reviewed all cases, the reaction conditions are rather hard compared with
NPN complexes known from the literature until 2015. Since aminophosphines without Binam-backbone.
then some more chemistry of main-group and transition metals
Generally, the chiral compounds 1–3 possess rather low sol-
with NPN-ligands has been described.[11–13] This ligand was ubility in most organic solvents (e.g. 2 was found soluble only
synthesized by the Staudinger reaction of Ph2P–N(H)tBu with in C6D5Br for NMR studies). When the synthesis of 3 was
tBuN3. Synthesis of the precursor phosphonium salt species performed in THF, formation of an air-stable powdery solid,
was earlier described by Christau[3a] using the Kirsanov con- which is almost insoluble in all common organic solvents, was
densation. Yet, we have found that this method is not appli- observed. The composition of 3·THF was established by ele-
1
cable to the synthesis of iminophosphonamide species from mental analysis and H/31P NMR spectrum of very poor qual-
two different amines and in particular to the synthesis of enti- ity. Unexpectedly, performing the same reaction in toluene (at
tled bis-NPN species: tedious work-up, side products forma- 100 °C) instead of THF results in formation of a clear solution.
tion, and unacceptable low yields of the target compounds In this case, the proceeding of the reaction was continuously
were experienced.
monitored by 31P NMR spectroscopy. The isolated product
Here, we communicate on preparation of a new series of found to be solvent-free and possesses high solubility even
chiral bis-NPN ligands derived from chiral (R)-N,NЈ-bis(di- in aromatic hydrocarbons! Irreversible formation of insoluble
phenylphosphanyl)-1,1Ј-binaphthyl-2,2Ј-diamine (Binam-P). 3·THF was observed upon addition of THF to a toluene solu-
Notwithstanding to reports of Miyano et al.,[14] we faced diffi- tion of 3. The isolation of 3·THF and the crystal structure de-
culties trying to reproduce synthesis of the (R)-(+)-Binam-P on termination of 1·2DMSO (vide infra) showed a high tendency
larger scale; the reported metallation/phosphanylation of (R)- of these bis-NPN species to capture polar solvent molecules
(+)-Binam with nBuLi and Ph2PCl failed in our hands. All via N–H···O hydrogen bridges. Interestingly, due to the bifunc-
attempts to enhance the chemoselectivity of the phosphanyl- tional character and rigidity of the Binam backbone such
ation, varying the concentration, temperature and stoichio- formed solvates reveal an extremely low solubility, e.g. 3·THF
metry of the reagents were unsuccessful. The tedious multiple was not soluble enough to obtain highly resolved 31P NMR
crystallization of a bulk amount of the product is another draw- spectra or crystals of sufficient quality for performing XRD
back of this method. We found, that a simple one-pot protocol studies.
including addition of an excess of Et3N to a premixed solution
1
Compounds 1–3 were characterized by H, 31P NMR spec-
of Binam and Ph2PCl is superior to any other synthetic meth- troscopy, EI-MS, and elemental analysis. The 13C NMR spec-
ods towards Binam-P. Our optimized procedure is reproduc- tra were recorded for 1 and 3 showing sufficient solubility in
ible, requires no additional purification by chromatography C6D6. 31P NMR resonances of 1–3 are shifted to δP –12.7 (1),
and gives this target material in high yield of 85% (Scheme 1) –13.8 (2), –17.0 (3) ppm that is rather close to those of mono-
(see Experimental Section) Surprisingly, Miyano reported on NPN bis-alkyl species Ph2P(=N–tBu)N(H)tBu with δP
“… no detectable amount …” in preparation of Binam-P in –21.9 ppm[10] and particularly to mono-NPN bis-aryl species
THF from Binam and Ph2PCl with Et3N.[14a] Earlier, prepara- Ph2P(=N–Ar)N(H)Mes (Ar = Mes, Dipp; Mes = 2,4,6-
tion of Binam(PR2)2 (R = 3,5-Me2C6H3, cyclo-C6H11) was re- Me3C6H2) with δP –13.04 and –15.34 ppm, respectively.[11a]
1
ported in DCM using catalysis by 10 mol% of DMAP under
In H NMR spectra, the NH proton resonances for 1 and 2
similar reaction conditions.[15] This protocol using THF as a having aliphatic substituents at the terminal N atom are close
solvent was successfully applied also for other aromatic di- to each other and shifted to 2.86 and 2.56 ppm, respectively.
amines (e.g. 1,2-diaminobenzene, 3,4-diaminotoluene, and 1,8- The NH proton of 3 resonates at δ = 5.70 ppm. This value is
diaminonaphthaline).[16]
even more down-field shifted compared with those found in
Scheme 1. Synthesis of (R)-Binam-P and therefrom derived bis-NPN ligands 1–3.
Z. Anorg. Allg. Chem. 0000, 0–0
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Journal of Inorganic and General Chemistry
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Zeitschrift für anorganische und allgemeine Chemie
analogous N,NЈ-bis-aryl-substituted mono-NPN species
Experimental Section
Ph2P(=NAr)N(H)Mes (Ar = Mes, Dipp), 4.10 and 4.13 ppm,
respectively.[11a] The broadened NH resonance found for 2 is
rather typical for mono-iminophosphonamides (cf. with those
in Ph2P(=NtBu)N(H)tBu) suggesting an equilibrium of tauto-
mers in this case. Two-bond scalar couplings (2JHP) of 6.8 Hz
and 10.0 Hz were observed for NH protons of 1 and 3, respec-
tively, pointing out that tautomeric equilibrium in these cases
is hindered. Finally, the high-field chemical shifts in 1 and 2
strongly suggest the location of the proton at N-Alk group,
whereas its location in case of 3 remains uncertain.
Yellow crystals of 1, suitable for X-ray structure determi-
nation, were grown by very slow cooling of slightly oversatur-
ated solution of 1 in DMSO from 60 °C down to room tem-
perature (see Experimental Section). 1 crystallizes with two
molecules of DMSO (1·2DMSO) in the monoclinic space
group C2/c. Each of terminal H–N bonds is coordinated to
one disordered DMSO molecule. The molecular structure of
1·2DMSO is shown in Figure 1.
Synthesis of (R)-N,NЈ-bis(diphenylphosphanyl)-1,1Ј-binaphthyl-
2,2Ј-diamine (Binam-P): To a stirred slurry of (R)-Binam (3.00 g,
10.6 mmol) in dry dichloromethane (90 mL) pure Ph2PCl (5.00 g,
22.7 mmol, 2.14 equiv.) was added, whereupon a yellow solution turns
green-brownish. To thus obtained clear solution an excess of Et3N
(10 mL) was added via dropping funnel (CAUTION! Exothermic re-
action!). Due to formation of triethylammonium chloride, the reaction
mixture turns very thick. After stirring for 1 h all volatiles were re-
moved in vacuo and dry toluene (60 mL) was added. The solid salt
was filtered off, washed on filter with toluene (2ϫ20 mL) and to thus
obtained solution dry methanol (100 mL) was added. The mixture was
allowed to stay for crystallization in a fridge at +10 °C. The reaction
product precipitates as a microcrystalline solid that was collected by
filtration, washed with cold methanol (3ϫ5 mL) and dried in vacuo.
1
Yield: 85% (5.88 g). H NMR (CDCl3, 300.1 MHz, 300 K): δ = 4.88
2
(d, JHP = 8.1 Hz, 1 H, NH), 6.82 (m, 2 H, p-Ph), 6.87 (m, 1 H, 6-/7-
Naph), 6.93–6.96 (m, 4 H, m-Ph), 7.04 (m, 2 H, o-Ph), 7.07 (m, 1 H,
7-/6-Naph), 7.22 (m, 1 H, Naph), 7.21 – 7.24 (m, 2 H, o-Ph’), 7.58 (d,
3
2JHH = 8.0 Hz, 1 H, 5-Naph), 7.64 (d, JHP = 9.0 Hz, 1 H, 4-Naph),
8.11 (dd, 3JHH = 9.0, 3JHP = 4.0 Hz, 1 H, 3-Naph) ppm. 13C{1H} NMR
3
(CDCl3, 75.5 MHz, 300 K): δ = 115.6 (d, JCP = 2 Hz, 1-Naph),
(24 Hz, 3-Naph) 123.3, 124.8, 127.4, 128.5 – 129.0 (4–5 resonances),
4
129.4 (d, JCP = 1.5 Hz, 9-Naph), 130.3 (J = 1.6 Hz), 130.7, 131.0
(2ϫ d, 2JCP = 26 Hz, 2ϫ o-Ph‘/Ph), 134.2 (10-Naph), 140.8, 141 (2ϫ
1
2
d, JCP = 24 Hz, 2ϫ ipso-Ph), 144.0 (d, JCP = 18 Hz, 2-Naph) ppm.
31P{1H} NMR (CDCl3, 81.0 MHz, 300 K): δ = +27.6 ppm. EI-MS
(m/z): 468 (9) [MH – PPh2]+, 284 (34) [MH2– 2 PPh2]+, 267 (18)
[MH –NPPh2] +, 201 (7) [Ph2PNH2]+, 200 (8) [Ph2PNH]+, 186 (46)
[Ph2PH]+.
Synthesis of Binam(Ph2PN(H)tBu)2 (1): To a stirred solution of Bi-
nam-P (2.00 g, 3.06 mmol) in 20 mL THF, tBuN3 (1.10 g, 11.1 mmol,
3.64 equiv.) was added and the reaction mixture was refluxed for 15 h
(slow gas evolution), whereupon a colorless, microcrystalline solid
forms. Upon cooling to room temperature the precipitate was filtered
off and dried in vacuo. Yield: 98% (2.40 g). 1H NMR (C6D6,
2
300.1 MHz, 300 K): δ = 1.04 (s, 9 H, Me3C), 2.86 (d, JHP = 6.8 Hz,
1 H, HNCMe3), 6.60 (m, 2 H, Ar), 7.0 – 7.2 (m, 7 H, Ar), 7.4 – 7.8
Figure 1. Molecular structure of 1·2DMSO. Hydrogen atoms con-
nected to carbon atoms are omitted for clarity. Selected bond lengths /
Å and angles /°: C1–N1 1.388(3), P–N1 1.548(2), P–N2 1.656(2); N1–
P–N2 122.95(14), C1–C10–C10’–C1’ –94.1(5).
(m, 7 H, Ar) ppm. 13C{1H} NMR (C6D6, 75.5 MHz, 300 K): δ = 32.0
3
2
(d, JCP = 4 Hz, CMe3), 52.5 (d, JCP = 2 Hz, CMe3), 120.7 (CAr),
3
124.3 (CAr), 125.5 (d, JCP = 12 Hz, 2-CAr), 127.9 (d, JCP = 5.8 Hz,
m-Ph), 127.9, 129.7 (9-,10-CAr), 130.0, 130.3 (2ϫs, p-Ph), 132.0,
2
1
132.5 (2ϫd, JCP = 9.4 Hz, o-Ph), 134.1, 136.0 (2ϫd, JCP = 82 Hz,
In conclusion, we have succeeded to develop simple repro- ipso-Ph), 135.3 (d, JCP = 35 Hz, 2-CAr), 146.6 (1-CAr) ppm. 31P{1H}
NMR (C6D6, 81.0 MHz, 300 K):δ
=
–12.7 ppm. ESI-MS
ducible procedure to the Binam-P and the chiral (R)-Binam-P
was prepared in high yield. Using the Staudinger reaction with
three representative organic azides – tBuN3, Ad-N3 and
DippN3 – corresponding chiral bis-iminophosphonamide (bis-
NPN) ligands 1–3 with an axial chiral 1,1Ј-binaphthyl-back-
inMeOH(m/z): 795 (100) [MH]+, 740 (2) [MH2– CMe3]+, 398 (20)
[MH2]2+. C52H52N4P2 (794.96): calcd. C 78.57, H 6.59, N 7.05%;
found: C 79.01, H 6.57, N 6.98%.
Synthesis of Binam(PPh2N(H)Ad)2 (2): To a stirred solution of Bi-
bone were synthesized and characterized. The molecular struc- nam-P (1.13 g, 1.73 mmol) in toluene (20 mL), AdN3 (0.65 g,
3.7 mmol, 2.14 equiv.) was added at ones. By heating to 80–90 °C
slow reaction with gas evolution takes place, accompanied with color
change of the reaction mixture to deep yellow. After ca. 30 min a
formation of precipitate started. The mixture was stirred at this tem-
perature overnight. It was filtered off, washed twice with the same
solvent and dried in vacuo. The product is poorly soluble in acetone,
DCM, CHCl3, and toluene. The compound is soluble in hot PhBr only.
Yield: 87% (1.43 mmol). 1H NMR (C6D5Br, 300.1 MHz, 300 K): δ =
1.00 (m, 6 H, Ad), 1.35 (m, 3 H, HC(CH2)3), 1.45 (m, 6 H, Ad), 2.56
(br. s, 1 H, N(H)Ad), 6.03 – 7.70 (m, 16 H, Ar, Ph) ppm. 13C{1H}
NMR(C6D5Br): no data available due to low solubility. 31P{1H} NMR
ture of (R)-Binam(Ph2PN(H)tBu)2 (1) as a solvate with two
DMSO molecules was determined by XRD. On example of 3,
formation of very stable, almost insoluble 1:1 solvate with
THF, 3·THF, was shown. Contrastingly to the known chiral
non-protic NPN superbases,[8] these bis-NPN species have
both basic N and acidic NH groups, proven by solvate forma-
tion, making them promising for asymmetric (organo)catalysis
and in design of new chiral C2-symmetric organometallic com-
plexes, e.g. chelating pendants to ansa-metallocenes for vari-
ous catalytic processes.
Z. Anorg. Allg. Chem. 0000, 0–0
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Journal of Inorganic and General Chemistry
SHORT COMMUNICATION
Zeitschrift für anorganische und allgemeine Chemie
(C6D5Br, 81.0 MHz, 300 K): δ = –13.8 ppm. EI-MS (m/z): 950 (56)
References
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H 6.78, N 5.89%; found: C 80.56, H 6.81, N 5.94%.
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Synthesis of Binam(PPh2N(H)Dipp)2 (3): To a stirred solution of
Binam-P (5.76 g, 8.83 mmol) in 50 mL toluene, DippN3 (3.80 g,
18.7 mmol, 2.12 equiv.) was added and heated at 100 °C for 15 h (slow
gas evolution). The reaction proceeding was monitored by 31P NMR
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1
tion of 3·THF solvate, which was identified only by H and 31P NMR
spectroscopy and elemental analysis, due to very low solubility in all
common organic solvent. 1H NMR (C6D6, 300.1 MHz, 300 K): δ =
3
3
0.92, 1.07 (2ϫd, JHH = 7.1 Hz, 2ϫ6 H,Me2CH), 3.50 (sept, JHH
=
2
7.1 Hz, 2 H, Me2CH), 5.70 (d, JHP = 10 Hz, 1 H, N(H)), 6.70–7.10
(m, 9 H, Ar), 7.35– 7.50 (m, 4 H, Ar), 7.86 (m, 2 H, o-Ph), 7.98 (d,
J = 8.9 Hz, 1 H, o-Ph) ppm. 13C{1H} NMR (C6D6, 75.5 MHz, 300 K):
δ = 23.7, 23.8 (2ϫs, Me2CH), 28.9 (Me2CH), 116.1 (d, JCP = 8.7 Hz,
2-CAr), 119.0 (p-Dipp), 120.5(CAr), 123.1 (m-Dipp), 124.3 (CAr), 124.9
(CAr), 129.9 (d, JCP = 6.3 Hz, p-Ph), 131.1 (d, JCP = 9.8 Hz, o-Ph),
131.2, 131.7,132.7 (d, JCP = 9.8 Hz, o-Ph’), 133.3, 134.2, 139.8 (CDipp
CHMe2), 142.0 (d, JCP = 7.5 Hz, ipso-Dipp), 143.4 ppm. 31P{1H}
NMR (C6D6, 81.0 MHz, 300 K): –17.0 ppm. C68H68N4P2
(1003.27): calcd. C 81.41, H 6.83, N 5.58%; found: C 81.18, H 7.00,
N 5.78%.
-
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δ
=
X-ray Diffraction: Data were collected with a STOE IPDS1 dif-
fractometer using graphite monochromated Mo-Kα radiation (λ =
0.71073 Å) at 180(2) K. The structures were solved by direct methods
using and SHELXS-97[17a] and refined by full-matrix least-squares on
F2 Fourier syntheses using SHELXL-2014/7[17b] software. The
hydrogen atoms were introduced at calculated positions using a riding
model. The program Diamond 3.1c was used for structure representa-
tions.[18]
Crystal Data for 1·2DMSO: C56H64N4O2S2P2, Mr = 951.17, mono-
clinic, space group C2/c, a = 19.129(2) Å, b = 9.7850(10) Å, c =
27.595(5) Å, β = 91.98(2)°, V = 5162.1(12) Å3, Z = 4, dcalcd
=
[10] K. A. Rufanov, N. K. Pruß, J. Sundermeyer, Dalton Trans. 2016,
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1.224 g·cm–3, μ = 0.210 mm–1, F(000) = 2024, R1 = 0.0514 [from 2443
unique reflections with I Ͼ 2σ(I)], wR2 = 0.1105 [for all 4091 unique
reflections], GooF = 0.891.
Crystallographic data (excluding structure factors) for the structure in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
number CCDC-1414731 for 1·2DMSO (Fax: +44-1223-336-033;
E-Mail: deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk)
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Acknowledgements
K. A. R. thanks the Deutscher Akademischer Austausch Dienst
(DAAD) for funding of a research fellowship at Philipps-Universität
Marburg within the Ostpartnerschaftsprogramm.
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Keywords: Staudinger reaction; Iminophosphonamide
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Received: December 12, 2018
Published Online: ᭿
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K. A. Rufanov,* I. Yu Titov, A. R. Petrov, K. Harms,
J. Sundermeyer .................................................................. 1–6
Synthesis of Binam-P Derived C2-Symmetric
bis-Iminophosphonamide Ligands. Molecular Structure of
[(R)-Binam(Ph2PN(H)tBu)2]
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