The formation of mesitylphosphine and dimesitylphosphine in the reaction of organonickel σ-complex [NiBr(Mes)(bpy)] (Mes = 2,4,6-trimethylphenyl, bpy = 2,2′-bipyridine) with phosphine PH3

Article abstract of DOI:10.1080/10426507.2020.1756289

The reactivity of the previously reported organonickel σ-complex [NiBr(Mes)(bpy)], where Mes = 2,4,6-trimethylphenyl, bpy = 2,2′-bipyridine, toward phosphine PH₃ was investigated. The reaction leads to primary mesitylphosphine MesPH₂

Full text of DOI:10.1080/10426507.2020.1756289

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: https://www.tandfonline.com/loi/gpss20
The formation of mesitylphosphine and
dimesitylphosphine in the reaction of organonickel
σ-complex [NiBr(Mes)(bpy)] (Mes = 2,4,6-
trimethylphenyl, bpy = 2,2′-bipyridine) with
phosphine PH3
Zufar N. Gafurov, Il’yas F. Sakhapov, Alexey A. Kagilev, Artyom O. Kantyukov,
Khasan R. Khayarov, Oleg G. Sinyashin & Dmitry G. Yakhvarov
To cite this article: Zufar N. Gafurov, Il’yas F. Sakhapov, Alexey A. Kagilev, Artyom O. Kantyukov,
Khasan R. Khayarov, Oleg G. Sinyashin & Dmitry G. Yakhvarov (2020): The formation of
mesitylphosphine and dimesitylphosphine in the reaction of organonickel σ-complex [NiBr(Mes)
(bpy)] (Mes = 2,4,6-trimethylphenyl, bpy = 2,2′-bipyridine) with phosphine PH3, Phosphorus, Sulfur,
and Silicon and the Related Elements, DOI: 10.1080/10426507.2020.1756289
To link to this article: https://doi.org/10.1080/10426507.2020.1756289
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PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
https://doi.org/10.1080/10426507.2020.1756289
The formation of mesitylphosphine and dimesitylphosphine in the reaction of
organonickel r-complex [NiBr(Mes)(bpy)] (Mes ¼ 2,4,6-trimethylphenyl, bpy ¼
2,20-bipyridine) with phosphine PH3
Zufar N. Gafurova, Il’yas F. Sakhapova, Alexey A. Kagilevb, Artyom O. Kantyukovb, Khasan R. Khayarovb, Oleg G.
Sinyashina, and Dmitry G. Yakhvarova,b
b
aArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Kazan, Russia; Kazan Federal University,
Kazan, Russia
ABSTRACT
ARTICLE HISTORY
Received 3 November 2019
Accepted 10 March 2020
The reactivity of the previously reported organonickel r-complex [NiBr(Mes)(bpy)], where Mes ¼
2,4,6-trimethylphenyl, bpy ¼ 2,20-bipyridine, toward phosphine PH3 was investigated. The reaction
leads to primary mesitylphosphine MesPH2 as the main product and dimesitylphosphine Mes2PH
as secondary product with the nickel complex as transmetalating agent. The formed MesPH2
reacts with an excess of the complex giving Mes2PH as the major product.
KEYWORDS
Phosphine PH3;
mesitylphosphine; dimesityl-
phosphine; organonickel
r-complexes;
GRAPHICAL ABSTRACT
transmetalation
Introduction
electrochemical activation and functionalization for the
preparation of organometallic reagents is very promising.[19]
Thus, the use of electrochemically generated organonickel
r-complexes[19–23] for obtaining of organophosphines is a
good alternative to classical chemical methods.
Organonickel r-bonded complexes are known as key inter-
mediates in various electrocatalytic processes of C–C and C–P
bond formation with participation of organic halides, chloro-
phosphines, and elemental (white) phosphorus when nickel
complexes with imine ligands have been used.[23,24] In some
cases these intermediates have been isolated, characterized by
X-ray diffraction and studied in different processes, including
catalytic ethylene oligomerization, formation of organophos-
phorus compounds directly from elemental (white) phos-
phorus and some others.[19,20,22,25]
A wide range of applications of trivalent phosphorus deriva-
tives in catalysis is a major driving force in the development
of the chemistry of C–P bonded compounds.[1–7] Primary
and secondary phosphines and their complexes are useful
synthetic intermediates and precursors for a variety of
chemical reactions with participation of organophosphorus
compounds.[8–14] Moreover, they have been nicely applied
for stereoselective synthesis of asymmetric tertiary phos-
phines and in the syntheses of macrocyclic phosphine
ligands.[15,16]
The treatment of organolithium or organomagnesium
reagents with corresponding halophosphines is a major
practical synthetic route to primary and secondary phos-
phines.[17] Currently, the development of new industrially
applicable synthetic methods for the synthesis of organo-
phosphorus compounds avoiding the use of halogenated,
low-stable and flammable reagents[18] is one of the main pri-
ority directions of modern chemical science and technology.
Previously we have shown the possibility of secondary aryl-
phosphines (mesitylphenylphosphine and dimesitylphosphine)
formation in the reaction of organonickel r-complex
[NiBr(Mes)(bpy)] with phenylphosphine.[22] This reaction pro-
ceeds with formation of a new carbon–phosphorus bond involv-
Interestingly, the use of alternative new techniques like ing the mesityl fragment of the starting organonickel r-complex.
CONTACT Dmitry G. Yakhvarov
ß 2020 Taylor & Francis Group, LLC
yakhvar@iopc.ru
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Kazan, Russia.

2
Z. N. GAFUROV ET AL.
N
N
1
PH3
H
P
H
Ni
P
H
- Ni complex,
- HBr
Br
- Ni complex,
- HBr
1
2
3
Scheme 1. Reaction of phosphine (PH3) with organonickel r-complex [NiBr(Mes)(bpy)].
1
Herein we present new results describing the preparation C6D6, 25 ꢀC) d ¼ 6.68 (s, 4H, meta-H), 5.42, (d, JPH
¼
of mesitylphosphine MesPH2 and dimesitylphosphine 229 Hz, 1H, PH), 2.19 (s, 12H, ortho-Me), 2.04 (s, 6H,
Mes2PH directly from inorganic phosphine PH3 and organo- para-Me).
nickel complex [NiBr(Mes)(bpy)], where Mes ¼ 2,4,6-trime-
Reaction of mesitylphosphine MesPH2 with organonickel
r-complex [NiBr(Mes)(bpy)]. MesPH2 (55 mg, 0.36 mmol)
has been added to a solution containing 166 mg (0.40 mmol)
of 1 in 10 mL of toluene. The resulting mixture was allowed
for stirring at room temperature for 24 h. The color of the
solution changed from deep red to black. Then the solvent
was evaporated and dimesitylphosphine 3 was extracted
from the residual mixture with pentane and dried in vac-
uum. It was obtained 65 mg of Mes2PH (yield 67%).
thylphenyl, bpy ¼ 2,20-bipyridine.
Experimental
Safety note.
CAUTION: Phosphine PH3 as well as primary and secondary
phosphines are toxic and hazardous compounds. The acciden-
tal exposure can lead to pulmonary edema and to death.
They can be absorbed either by inhalation or transdermally
and, as respiratory poisons, affect the transport of oxygen or
interfere with the utilization of oxygen by various cells in the
Results and discussion
body. The phosphines are heavier than air, so they stay and The organonickel r-complex [NiBr(Mes)(bpy)] (1) was pre-
are distributed nearer to the floor. All the reactions and han- pared according to an earlier developed procedure,[19] which
dling of these compounds should be carried out under an includes oxidative addition of the electrochemically gener-
inert atmosphere in a well-ventilated hood. In case of emer- ated [Ni0(bpy)] complex to mesitylbromide (MesBr).
gency, organic phosphines can be treated and neutralized Previously we demonstrated the interaction of this electro-
with aqueous hydrogen peroxide solution.
chemically synthesized nickel complex with nitriles, which
All manipulations and reactions were carried out under leads to the formation of imines of general formula
inert atmosphere of dry nitrogen. Organonickel r-complex R(Mes)C ¼ NH as the result of C–C coupling reaction.[29]
[NiBr(Mes)(bpy)][19] and phosphine PH3[26]were obtained Thus, we here continue our work on organonickel chemistry
by described procedures. The NMR spectra were recorded and expand the examples of the use of organonickel
with
spectrometer.
a
high-resolution Bruker Avance III 400 MHz r-complexes as reagents in organic synthesis.
We have found that interaction of complex 1 with an excess
Reaction of phosphine (PH3) with organonickel r-complex of phosphine PH3 continuously bubbled through a toluene solu-
[NiBr(Mes)(bpy)]. PH3 was generated from white phos- tion of 1 at room temperature results in the formation of mesityl-
phorus (20 mmol) according to a literature procedure.[26]The phosphine MesPH2 (2) and dimesitylphosphine Mes2PH (3)
flow of the mixture PH3/N2 was bubbled through a solution (Scheme 1). The nickel complex 1 plays the role of a transmeta-
containing 1 (467 mg, 1.13 mmol) in toluene (30 mL) for 5 h lating agent in this reaction. However, performing this transme-
at room temperature with continuous stirring. After that the talation reaction catalytically with MesBr and PH3 as the reagents
mixture was allowed to stir for 50 h at room temperature. and 1 as catalyst was impossible due to the precipitation of
The color of the solution changed from deep red to black. unidentified nickel containing by-product. Further optimization,
Then, the volatiles were evaporated from the mixture under including the test of different solvents and applying of electro-
vacuum and mesitylphosphine 2 was isolated by vacuum chemical methods, which may give more insight into the mech-
distillation (65 ꢀC, 0.001 Torr). It was obtained 55 mg (yield anism of this interaction, is under investigations.
32%) of MesPH2 (2). Dimesitylphosphine was extracted
It was found, that the mesitylphosphine 2 formed is cap-
from the residual oil with pentane and dried. It was isolated able to react with excess of 1 yielding the secondary dimesi-
with a yield of 40 mg (13%) of Mes2PH (3). The physico- tylphosphine 3. However, the formation of tertiary
chemical characteristics of the obtained mesitylphosphine trimesitylphosphine Mes3P was not observed even in case of
2[27,28] and dimesitylphosphine 3[22,28] are in agreement high excess of organonickel r-complex 1.
It should be noted that mesitylphosphine 2 is air sensitive and
with the literature data.
31
Mesitylphosphine (2): P NMR (121.4 MHz, C6D6, 25 ꢀC): undergoes oxidation when kept in air to give mesitylphosphine
d ¼ ꢁ155.8 (t, JPH ¼ 203 Hz). H NMR (300.0 MHz, C6D6, oxide MesP(O)H2 (31P NMR, d: ꢁ14.4 ppm, t, JPH ¼ 474 Hz)
1
1
1
1
25 ꢀC): d ¼ 6.63 (s, 2H, meta-H), 3.53, (d, JPH ¼ 203 Hz, and the corresponding mesitylphosphinic acid MesP(O)(OH)H
1
2H, PH), 2.17 (s, 6H, ortho-Me), 2.03 (s, 3H, para-Me).
(31P NMR, d: 24.5 ppm, d, JPH ¼ 556 Hz),[30] while dimesityl-
Dimesitylphosphine (3): 31P NMR (121.4 MHz, C6D6, phosphine 3 is air stable due to steric hindrance by two mesityl
25 ꢀC) d ¼ ꢁ92.9 (d, JPH ¼ 229 Hz). H NMR (300.0 MHz, substituents together with its electronic nature.[31]
1
1

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
3
Moiety as a PH Protecting Group in the Synthesis of a
Phosphino Macrocycle That Contains a Secondary-Phosphino
Ligating Site. Inorg. Chem. 1985, 24, 1613–1616. DOI: 10.1021/
ic00205a005.
Conclusions
Thus, a new method for the synthesis of primary and sec-
ondary arylphosphines, namely mesitylphosphine MesPH2
and dimesitylphosphine Mes2PH, respectively, directly from
[11] Ficks, A.; Martinez-Botella, I.; Stewart, B.; Harrington, R. W.;
Clegg, W.; Higham, L. J. Taming Functionality: Easy-to-Handle
Chiral Phosphiranes. Chem. Commun. 2011, 47, 8274–8276.
DOI: 10.1039/c1cc12440d.
[12] Ficks, A.; Hiney, R. M.; Harrington, R. W.; Gilheany, D. G.;
Higham, L. J. MOP-Phosphonites: A Novel Ligand Class for
Asymmetric Catalysis. Dalton Trans. 2012, 41, 3515–3522. DOI:
10.1039/c2dt12214f.
[13] Ficks, A.; Harrington, R. W.; Higham, L. J. Chiral MOP-
Phosphonite Ligands: Synthesis, Characterisation and
Interconversion of g1,g6-(r-P, p-arene) Chelated Rhodium(I)
Complexes. Dalton Trans. 2013, 42, 6302–6305. DOI: 10.1039/
c3dt50482d.
[14] Fleming, J. T.; Ficks, A.; Waddell, P. G.; Harrington, R. W.;
Higham, L. J. The Design of Second Generation MOP-
Phosphonites: Efficient Chiral Hydrosilylation of Functionalised
Styrenes. Dalton Trans. 2016, 45, 1886–1890.
phosphine
PH3
and
organonickel
r-complex
[NiBr(Mes)(bpy)] has been elaborated. The method involves
the use of P-H containing precursors as the starting reagents
and avoids the use and formation of ecologically dangerous
chloro-derivatives. This can be considered as a new powerful
tool for the preparation of organophosphorus compounds
containing C–P bonds. The extension of the range of syn-
thetic possibilities of organonickel r-complexes of this type,
including the preparation of asymmetric organic phosphines
in catalytic conditions, is currently in the progress.
Disclosure statement
No potential conflict of interest was reported by the authors.
[15] Nell, B. P.; Tyler, D. R. Synthesis, Reactivity, and Coordination
Chemistry of Secondary Phosphines. Coord. Chem. Rev. 2014,
279, 23–42.
Funding
[16] Adjabeng, G.; Brenstrum, T.; Wilson, J.; Frampton, C.;
Robertson, A.; Hillhouse, J.; McNulty, J.; Capretta, A. Novel
Class of Tertiary Phosphine Ligands Based on a Phospha-
Adamantane Framework and Use in the Suzuki Cross-Coupling
Reactions of Aryl Halides under Mild Conditions. Org. Lett.
2003, 5, 953–955.
This work is financially supported by the Russian Science Foundation
(project 18-13-00442).
[17] Allen, D. W. Phosphines and Related C-P Bonded Compounds.
Organophosphorus Chem. 2016, 45, 1–50. DOI: 10.1039/
9781782626930-00001.
[18] Gafurov, Z. N.; Kagilev, A. A.; Kantyukov, A. O.; Sinyashin,
O. G.; Yakhvarov, D. G. Hydrogenation Reaction Pathways in
Chemistry of White Phosphorus. Pure Appl. Chem. 2019, 91,
797–810. DOI: 10.1515/pac-2018-1007.
[19] Yakhvarov, D. G.; Trofimova, E. A.; Rizvanov, I. K.; Fomina,
O. S.; Sinyashin, O. G. Electrochemical Synthesis and Catalytic
Activity of Organonickel r-Complexes. Russ. J. Electrochem.
2011, 47, 1100–1110. DOI: 10.1134/S1023193511100247.
[20] Yakhvarov, D. G.; Kvashennikova, S. V.; Sinyashin, O. G.
Reactions of Activated Organonickel r-Complexes with
Elemental (White) Phosphorus. Russ. Chem. Bull. 2013, 62,
2472–2476.
[21] Gafurov, Z. N.; Sinyashin, O. G.; Yakhvarov, D. G.
Electrochemical Methods for Synthesis of Organoelement
Compounds and Functional Materials. Pure Appl. Chem. 2017,
89, 1089–1103. DOI: 10.1515/pac-2017-0202.
References
[1] Peruzzini, M.; Gonsalvi, L. Phosphorus Compounds: Advanced
Tools in Catalysis and Material Sciences. Springer: Berlin, 2011.
DOI: 10.1007/978-90-481-3817-3.
[2] Caporali, M.; Serrano-Ruiz, M.; Peruzzini, M. Benign Chlorine-
Free Approaches to Organophosphorus Compounds. In
Chemistry Beyond Chlorine; Tundo, P., He, L.N., Lokteva, E.,
Mota, C., eds., Springer: Cham, 2016; pp. 97–136. DOI: 10.
1007/978-3-.319-30073-3_3.
[3] Quin, L. D. A Guide to Organophosphorus Chemistry. Wiley:
New York, 2000. ISBN: 978-0- 471-31824-8.
[4] Katti, K. V.; Gali, H.; Smith, C. J.; Berning, D. E. Design and
Development of Functionalized Water-Soluble Phosphines:
Catalytic and Biomedical Implications. Acc. Chem. Res. 1999,
32, 9–17. DOI: 10.1021/ar9800082.
[5] Gali, H.; Hoffman, T. J.; Sieckman, G. L.; Owen, N. K.; Katti,
K. V.; Volkert, W. A. Synthesis, Characterization, and Labeling
with 99mTc/188Re of Peptide Conjugates Containing a Dithia-
Bisphosphine Chelating Agent. Bioconjugate Chem. 2001, 12,
354–363. DOI: 10.1021/bc000077c.
[6] Dorn, H.; Singh, R. A.; Massey, J. A.; Lough, A. J.; Manners, I.
Rhodium Catalyzed Formation of Phosphorus–Boron Bonds:
Synthesis of the First High Molecular Weight Poly
(Phosphinoborane). Angew. Chem. Int. Ed. 1999, 38,
[22] Gafurov, Z. N.; Musin, L. I.; Sakhapov, I. F.; Babaev, V. M.;
Musina, E. I.; Karasik, A. A.; Sinyashin, O. G.; Yakhvarov,
D. G. The Formation of Secondary Arylphosphines in the
Reaction of Organonickel r-Complex [NiBr(Mes)(bpy)], Where
Mes ¼ 2,4,6- Trimethylphenyl, bpy ¼ 2,2’-Bipyridine, with
Phenylphosphine. Phosphorus Sulfur Silicon Relat. Elem. 2016,
191, 1475–1477.
3321–3323.
DOI:
10.1002/(SICI)1521-
[23] Yakhvarov, D. G.; Khusnuriyalova, A. F.; Sinyashin, O. G.
Electrochemical Synthesis and Properties of Organonickel
r-Complexes. Organometallics 2014, 33, 4574–4589. DOI: 10.
1021/om500100q.
[24] Klein, A.; Budnikova, Y. H.; Sinyashin, O. G. Electron Transfer
in Organonickel Complexes of a-Diimines: Versatile Redox
Catalysts for C–C or C–P Coupling Reactions – A Review. J.
Organomet. Chem. 2007, 692, 3156–3166. DOI: 10.1016/j.jor-
ganchem.2007.01.021.
[25] Yakhvarov, D. G.; Tazeev, D. I.; Sinyashin, O. G.; Giambastiani,
G.; Bianchini, C.; Segarra, A. M.; L€onnecke, P.; Hey-Hawkins,
E. Electrochemical Synthesis of the r-Aryl Complex
[NiBr(Mes)(bpy)] and Its Use as Catalyst Precursor for the
3773(19991115)38:22 < 3321::AID-ANIE3321 > 3.0.CO;2-0.
[7] Limburg, C.; Gomez-Ruiz, S.; Hey-Hawkins, E. A Sodium
Ferrocenyl-Phosphanide Polymer Based on Racemic Primary
Aminoalkyl (Bisphosphanyl) Ferrocene. Dalton Trans. 2010, 39,
7217–3219.
[8] Maier, L. Preparation and Properties of Primary, Secondary,
and Tertiary Phosphines. Prog. Inorg. Chem. 1963, 5, 27–210.
DOI: 10.1002/9780470166062.ch2.
[9] Hanaya, T.; Yamamoto, H. Synthesis and Structural Analysis of
4-Deoxy-4-(Hydroxyphosphinyl and Phenylphosphinyl)-D-
Ribofuranoses. Bull. Chem. Soc. Jpn. 1989, 62, 2320–2327.
[10] Kyba, E. P.; Liu, S. T. Phosphino Macrocycles. 140. Synthesis of
Unusual Phosphine Ligands. Use of the 1-Naphthylmethyl

4
Z. N. GAFUROV ET AL.
Oligomerization of Ethylene (Mes ¼ 2,4,6-trimethylphenyl, bpy [29] Gafurov, Z. N.; Sakhapov, I. F.; Babaev, V. M.; Dobrynin, A. B.;
¼ 2,2’-bipyridine). Polyhedron 2006, 25, 1607–1612.
Kurmaz, V. A.; Metlushka, K. E.; Rizvanov, I. K.;
Shaikhutdinova, G. R.; Sinyashin, O. G.; Yakhvarov, D. G.
Study of the Reactivity of Organonickel r-Complexes towards
Nitriles. Russ. Chem. Bull. 2017, 66, 254–259. DOI: 10.1007/
s11172-017-1725-8.
[26] Toy, A. D. F. The Chemistry of Phosphorus; Pergamon Press:
Oxford, UK, 1973. ISBN: 9781483139593.
[27] Masuda, J. D.; Jantunen, K. C.; Ozerov, O. V.; Noonan, K. J.;
Gates, D. P.; Scott, B. L.; Kiplinger, J. L. A Lanthanide
Phosphinidene Complex: Synthesis, Structure, and Phospha- [30] Yakhvarov, D.; Trofimova, E.; Sinyashin, O.; Kataeva, O.;
€
Wittig Reactivity. J. Am. Chem. Soc. 2008, 130, 2408–2409.
DOI: 10.1021/ja7105306.
[28] Pal, K.; Hemming, O. B.; Day, B. M.; Pugh, T.; Evans, D. J.;
Layfield, R. A. Iron and Cobalt Catalyzed Synthesis of Carbene
Budnikova, Y.; LoNnecke, P.; Hey-Hawkins, E.; Petr, A.;
Krupskaya, Y.; Kataev, V.; et al. New Dinuclear Nickel(II)
Complexes: Synthesis, Structure, Electrochemical, and Magnetic
Properties. Inorg. Chem. 2011, 50, 4553–4558.
Phosphinidenes. Angew. Chem. Int. Ed. 2016, 55, 1690–1693. [31] Stewart, B.; Harriman, A.; Higham, L. J. Predicting the Air
DOI: 10.1002/anie.201508303.
Stability of Phosphines. Organometallics 2011, 30, 5338–5343.
DOI: 10.1021/om200070a.