Zirconium-catalyzed alkene cycloalumination for the synthesis of substituted phosphines and their transition metal (Mo, Pd) complexes

Article abstract of DOI:10.1016/j.jorganchem.2016.10.012

An original method for the synthesis of substituted phosphines R₂P(X)BuR^′(R^′?=?n-Hex, Bn, napht, cyclo-Hex) and R₂P(X)EtR^′(R^′?=?2-bycyclo[2.2.1]hept-2-yl) (R?=?Et, Ph, X?=?O, S), in 65–72%

Full text of DOI:10.1016/j.jorganchem.2016.10.012

Journal of Organometallic Chemistry 824 (2016) 73e79
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Zirconium-catalyzed alkene cycloalumination for the synthesis of
substituted phosphines and their transition metal (Mo, Pd) complexes
Leisan К. Dil'mukhametova, Vladimir А. D'yakonov*, Тat'yana V. Tyumkina**,
Usein
М. Dzhemilev
Institute of Petrochemistry and Catalysis of Russian Academy of Sciences, 141 Prospekt Oktyabrya, Ufa 450075, Russian Federation
a r t i c l e i n f o
a b s t r a c t
An original method for the synthesis of substituted phosphines R2P(X)BuR′ (R′ ¼ n-Hex, Bn, napht, cyclo-
Hex) and R2P(X)EtR′ (R′ ¼ 2-bycyclo[2.2.1]hept-2-yl) (R ¼ Et, Ph, X ¼ O, S), in 65e72% yield has been
developed via the interaction between halophosphines R2PCl (R ¼ Et, Ph) and aluminacyclopentanes,
generated in situ from alkenes and Et3Al in the presence of Cp2ZrCl2. The synthesized phosphines were
found to react with Mo(CO)6 giving rise to molybdenum complexes Mo(CO)5L (L ¼ 4a; 3b; 3c). The
interaction between (2-bicyclo[2.2.1]hept-2-ylethyl)diphenylphosphine and Pd(COD)Cl2 leads to com-
pound of the type L2PdCl2. Structures of new compounds were determined using X-ray diffraction
techniques and multinuclear (1H, 13C, and 31P) NMR spectroscopy.
Article history:
Received 5 March 2016
Received in revised form
29 September 2016
Accepted 5 October 2016
Available online 6 October 2016
Keywords:
Cycloalumination
Aluminacyclopentane
Phosphine oxide
Phosphine
© 2016 Elsevier B.V. All rights reserved.
Molybdenum complex
Palladium complex
1. Introduction
corresponding cyclic five-membered OPC with high yields
(80e90%) [27e31].
Organophosphorous compounds (OPC) continue to be attractive
due to diverse applications thereof in organic and elementoorganic
chemistry as the reagents for organic synthesis, precursors of bio-
logically active compounds [1e4], and components of catalytic
systems for homogeneous metal complex catalysis [5e18]. The
nature and structure of the ligand as a part of the catalytic system is
one of the most important factors, which define stereo- and
regioselectivity of the reaction. Therefore, the development of the
new and efficient approaches to the synthesis of phosphines
(phosphine ligand) of specified structure is an actual problem.
Among the wide variety of approaches to the carbon-
phosphorous bond formation [8,19e26], the interaction between
organometallics and phosphorous halides is one of the simple and
convenient methods. We have recently shown that the in situ
interaction of aluminacarbocycles, being synthesized through the
In the development of these investigations we have put forward
one-pot synthetic strategy to prepare substituted 1,4-
bis(phosphino)butanes by the reaction between di-substituted
organophosphorous(III) monohalides and aluminacyclopentanes
involving both AleC bonds [32,33].
In this paper, we report on our efforts to produce new types of
phosphines and transition metal complexes thereof as promising
ligands for metal complex catalysis [8,10,14].
a
2. Results and discussion
2.1. Synthesis and structure of substituted phosphineoxides,
phosphinesulfides and phosphines
Our studies have shown that the reaction of dialkyl- or diphe-
catalytic cycloalumination of
a-olefins, norbornenes, and acety-
nylphosphorus chlorides R2PCl (R
nacyclopentanes 1 provides phosphines 3 involving exclusively the
AleC bond located at C(5) carbon atom.
¼
Ph, Et) with alumi-
lenes-, with alkyl(phenyl)phosphorus(III) dihalides led to the
Thus, the interaction between diphenylphosphine chloride and
3-hexylaluminacyclopentane 1a in situ generated in the cyclo-
alumination reaction of 1-octene with AlEt3 in the presence of
Cp2ZrCl2 (~20e22 ꢀС, 6 h), after hydrolysis of the reaction mixture,
* Corresponding author.
** Corresponding author.
E-mail address: DyakonovVA@gmail.com (V.А. D'yakonov).
http://dx.doi.org/10.1016/j.jorganchem.2016.10.012
0022-328X/© 2016 Elsevier B.V. All rights reserved.

74
L.К. Dil'mukhametova et al. / Journal of Organometallic Chemistry 824 (2016) 73e79
was found to afford (3-methylnonyl)diphenylphosphine 3a. Sub-
sequent oxidation of 3a with H2O2 led to (3-methylnonyl)diphe-
molecule of dialkyl(aryl)phosphine chloride that implies pre-
liminary coordination of organophosphorus reagent to aluminum
in the initial aluminacyclopentane. In this way, owing to the
preferred intramolecular interactions between aluminum and
phosphorus as compared to intermolecular, the second AleC bond
remains inert.
nylphosphine oxide 5
а in 80% yield. Elemental sulfur reacted with
phosphorus under mild conditions (toluene, 40 ꢀС, 8 h) to form (3-
methylnonyl)diphenylphosphine sulfide 5а in 71% yield (Scheme
1).
In an analogous fashion, (3-methyl-4-phenylbutyl)diphenyl-
phosphine oxide 5b, (2-bicyclo[2.2.1]hept-2-ylethyl)diphenyl-
phosphine oxide 5c, (3-(2-naphthyl)butyl)diphenylphosphine
oxide 5d, (3-cyclohexylbutyl)diphenylphosphine oxide 5е, (3-
methylnonyl)diethylphosphine oxide 5f, a number of deutero-
substituted derivatives 6a,c,f, and also (2-(3-deuterobicyclo[2.2.1]
hept-2-ylethyl)diethylphosphine oxide 6g have been obtained from
aluminacyclopentanes 1 and corresponding diphenyl- and dieth-
ylphosphorus chlorides (Table 1).
This study has shown that attachment of dialkyl(aryl)phos-
phorus(III) chloride to aluminacarbocyсle 1 occurs by the more
sterically accessible AleC bond. It should be noted that all attempts
to involve the second molecule of R2PCl (R ¼ Ph, Et) in the above
reaction altering other reaction parameters (eg. the use of the
three-fold or five-fold excess of halophosphine, the elevated tem-
peratures within the interval 50e110 ꢀC, and also catalytic amounts
of CuCl, СuI [34,35], were unsuccessful.
Regioselective formation of diphenyl(diethyl)substituted phos-
phine oxides 5, 6 and phosphine sulfide 7 has been unambiguously
confirmed by the data of multinuclear 1Н, 13С, and 31Р NMR spec-
troscopy. Thus, the signals assigned to the methyl group on the C(3)
carbon atom at ~18e19 ppm in the 1H and 13С NMR spectra of
phosphine oxides 5а-b, 5d-f, and phosphine sulfide 7а indicate the
activity of only one AleC bond. In addition, the triplet C(10) signals
detected in the NMR spectra of products after deuterolysis of
diphenyl- or diethylphosphine oxides 6a and 6f as well as the
signals from the C(8) carbon atoms in the norbornene skeleton in
compounds 6c and 6g, may serve as the further support for this fact.
As the three-substituted phosphine oxides have the only single
phosphorus atom in the molecule, heteronuclear constants
J(31P-13C) were measured only for three С(1), С(2) and С(3) carbon
atoms, in this case, the maximum value of SSCC (JPC ~ 64e76 Hz)
corresponds to the carbon atom located in the
a position relative to
the heteroatom. It has been noticed that chemical shift of phos-
phorus in the diphenyl substituted phosphines occurs at low fre-
Apparently, the strong donating bond Р / Аl in the in situ
generated six-membered intermediate [(hexyl-, 2-bycyclo[2.2.1]
hept-2-yl)(diethylphosphino- or diphenylphosphino)ethyl] or
[(benzyl-, cyclohexyl)(diethylphosphino- or diphenylphosphino)
butyl] ethylaluminum chloride 2 causes the relative inertness of the
AleC(2) bond thus preventing incorporation of the second
quencies (
themselves at much higher frequencies (
responds to the literature data [36]. The intermediate value of
chemical shift (
P ¼ 43.44 ppm) was obtained for sulfide 7a.
The individual phosphine oxides 5 -f, 6 , 6c, 6f-g and phos-
phine sulfide 7 were isolated by column chromatography on SiO2
dP ~ 32e33 ppm), whereas their diethyl analogs manifest
dP 52e54 ppm) that cor-
d
а
а
а
with hexane:EtOAc:MeOH ¼ 5:3:1 as the eluent. These compounds
5a-e represent white crystals, 5f, 6f-g - colorless oils, and phos-
phine sulfide 7а was yellow oil. From a number of the phosphine
oxides synthesized, (2-bicyclo[2.2.1]hept-2-ylethyl)diphenylphos-
phine oxide 5c after crystallization from a mixture of methylene
chloride and hexane has been additionally studied by X-ray method
(Fig. 1).
Table 1
Reaction yields of the target substituted phosphines, phosphine oxides and phos-
phine sulfide.
Entry
Compound
R
R0
Yield (%)a
1
2
3
3a
3b
3c
Ph
Ph
Ph
n-Hex
Bn
69
72
70
4
5
3d
Ph
Ph
67
68
3е
6
7
8
9
4a
5a
5b
5c
Ph
Ph
Ph
Ph
n-Hex
n-Hex
Bn
65b
80
82
79
10
11
5d
5e
Ph
Ph
73
84
12
13
14
5f
6a
6c
Et
Ph
Ph
n-Hex
n-Hex
77
78b
76b
15
16
6f
6g
Et
Et
n-Hex
n-Hex
74b
72b
Fig. 1. Spatial structure of compound 5c. The atoms are represented by thermal vi-
bration ellipsoids (p
¼
50%). Main bond lengths (Å) and angles (deg):
P1eC10
C2eC3
C5eC6
C8eC3
¼
1.808(4), P1eC100
¼
1.801(4), P1eC1
1.560(9), C4eC5
1.788(11), C7eC8
111.63(17), O1eP1eC100
106.04(17), C1eP1eC10
¼
1.799(4), C1eC2
1.862(13), C4eC9
1.474(9), C7eC9
¼
1.544(6),
1.383(10),
1.263(10),
110.91(17),
107.02(18),
¼
1.552(6), C3eC4
1.322(10), C6eC7
¼
¼
¼
17
7a
Ph
71c
¼
¼
¼
¼
a
Isolated yields.
Deuterated products.
Phosphine sulfide.
¼
1.469(8), OeP1eC10
¼
¼
b
c
O1eP1eC1
¼
114.75(19), C100ꢁP1eC10
¼
¼
C1eP1eC100 ¼ 105.96(17), C2eC1eP1 ¼ 110.6(3), C1eC2eC3 ¼ 112.0(4).

L.К. Dil'mukhametova et al. / Journal of Organometallic Chemistry 824 (2016) 73e79
75
2.2. Synthesis of molybdenum and palladium complexes of
substituted phosphines
and С(10)] of the phosphine ligand.
3. Сonclusion
It is well known that the majority of transition metals form
stable phosphine complexes. In order to investigate binding prop-
erties of the synthesized OPC and the possibilities thereof as li-
In conclusion, we have developed a new original method for the
synthesis of acyclic phosphines via the interaction between dieth-
yl(diphenyl)phosphorus halides and aluminacyclopentanes gener-
ated in situ from alkenes and Et3Al in the presence of СpZrCl2 as the
catalyst. Based on phosphines synthesized, stable phosphine
complexes of Мо and Pd previously undescribed have been ob-
tained. The elaborated reaction opens up new ways for the direct
synthesis of acyclic phosphines of a definite structure, promising as
ligands for metal complex catalysts and precursors of potential
biologically active compounds.
gands, we have performed reduction of 5
hydride HSiCl3 (benzene, 80 ꢀC, 4 h) to obtain appropriate phos-
phines. Among them, 3 -с,e and 4a represent colorless paraffin-like
а-e and 6a using silicon
а
substances, and compound 3d is a white powder (Scheme 1). The
shift of the 31Р phosphorus signals attributable to the said com-
pounds toward extremely low frequency magnetic field
(
d
P ¼ ꢁ15 ppm) indicates the complete reduction of phosphines
tested. The presence of a lone electron pair on phosphorus
expectedly led to a decrease in the JPC values corresponding to
carbon atoms (to7e11 Hz) [36].
a-
4. Experimental
Complexes of the type Mo(CO)5L (L ¼ (3-deuteromethylnonyl)
diphenylphosphine, (3-methyl-4-phenylbutyl)diphenylphosphine,
4.1. General (instruments)
(2-bicyclo[2.2.1]hept-2-ylethyl)diphenylphosphine) 8
obtained from the reaction of molybdenum hexacarbonyl with
eqiumolar amounts of compounds 4 and 3b,c in tetrahydrofuran
а-с have been
Chromatographic analysis was performed on a Shimadzu GC-9A
instrument using a 2000 ꢂ 2 mm column, the SE-30 (5%) stationary
phase on Сhromaton N-AW-HMDS (0.125e0.160 mm), helium
carrier gas (30 mL/min), temperature programming from 50 to
300 ꢀС at a 8 ꢀС/min rate. IR spectra were recorded on Bruker
а
(80 ꢀC, 5 h) (Scheme 2). The reaction of (2-bicyclo[2.2.1]hept-2-
ylethyl)diphenylphosphine 3c with Pd(COD)Cl2 in methylene
dichloride (30e35 ꢀC, 5 h) provided bisphosphine complex (bis-[(2-
bicyclo[2.2.1]hept-2-ylethyl)diphenylphosphino]palladium
dichloride) 9 (Scheme 2).
VERTEX 70V using KBr discs over the range of 400e4000 cmꢁ1
.
Melting points were recorded on Stuart SMP3. The 1Н, 13С, and 31
P
Control over the complexation reaction between phosphine and
molybdenum carbonyl or (1,5-cyclooctadiene)palladium(II)
dichloride was carried out by a shift of the phosphorus signal in the
31P NMR spectra relative to the starting phosphine. Thus, phos-
NMR spectra were measured in CDCl3 on a Bruker Avance-400
spectrometer (100.62 MHz for 13C, 400.00 MHz for 1H, and
161.92 MHz for 31P). Mass spectra were run on a MALDI TOF/TOF
Autoflex-III Bruker instrument with 2,5-dihydroxybenzoic (2,5-
phine complexes of molybdenum 8а-c resonate in the region of
DHB) and
a-cyano-4-hydroxycinnanic acid (HCCA) matrix in the
~27 ppm, whereas complex 9 showed a signal at
d
P 16.68 ppm. The
reflection, positive ion mode. Elemental analysis of the samples was
determined by elemental analyzer firm Karlo Erba, model 1106. X-
ray diffraction analysis was performed on an XCaliburEos four-
molecular structures of these complexes have been confirmed by
one- and two-dimensional NMR spectroscopy. The observed mag-
netic equivalence of the C(1) carbon signals of initial phosphines 4a,
3b-c in the 13C spectra of compounds 8a-c indicates that the
phosphine ligand displaces only one molecule of CO in hex-
acarbonyl molybdenum. In the case of a structure having two
circle automated diffractometer (graphite monochromator, MoK
a
radiation,
l
¼ 0.71073 Å, 2qmax ¼ 62ꢀ). The data were collected and
treated using the CrysAlisPro Oxford Diffraction Ltd. program
package, version 1.171.36.20. The structures were solved by the
direct method and refined by the full-matrix least-squares method
in the anisotropic approximation for non-hydrogen atoms. The
hydrogen atoms were located on electron density maps and refined
in the isotropic approximation. The refinement was done using
SHELX97 program package [38]. TLC was performed on Silufol UV-
254 plates with hexaneeethyl acetateemethanol (5:3:1) mixture
as the eluent and I2 for visualization. For column chromatography,
Acros silica gel (0.060e0.200 mm) was used. Reactions with
phosphine ligands, the 13C signals of
a-carbon atoms of the said
ligand appear as a triplet, due to aliasing [31,37]. The IR spectra of
compounds 8a-c contain the absorption CO bands at 2070 (s) and
1987 (s) cmꢁ1, characteristic for mono-phosphine complexes of the
type Mo(CO)5L. This also confirms the structure of complexes above
[37]. The structure of complex 9 has been proposed on the basis of
elemental analysis and the data of the 13C NMR spectrum con-
taining the triplet signals attributable to the
a-carbon atoms [С(1)
'
R
'
R
H3O+
H2O2
R2P
R2P
HSiCl3
S8
X
5
'
R
'
R
3
(X = O)
4
3
Et3Al
R2PCl
7а (Х = S)
5
2
'
R
Cp2ZrCl2
Al
Al Cl
Et
P
R2
'
R
Et
'
R
D
D3O+
R2P
O
H2O2
D
1
2
R2P
4
6
R = Ph, R' = n-Hex (a); R = Ph, R' = Bn (b); R = Ph, R' =
R = Et, R' = n-Hex (f); R = Et, R' = (g)
(c); R = Ph, R' =
(d); R = Ph, R' =
(e);
Scheme 1.

76
L.К. Dil'mukhametova et al. / Journal of Organometallic Chemistry 824 (2016) 73e79
Mo(CO)6 (1eq)
THF, 80oC, 5h
4a
3b
[Mo(CO)5(4a)]
8a
Mo(CO)6 (1eq)
THF, 80oC, 5h
[Mo(CO)5(3b)]
8b
Ph2P
PPh2
Cl
Mo(CO)6 (1eq)
THF, 80oC, 5h
Pd(COD)Cl2
3c
[Mo(CO)5(3c)]
CHCl2,30-35oC, 5h
Pd
8c
Cl
9
Scheme 2.
organometallic compounds were performed in a dry argon flow.
The solvents were dried and distilled immediately prior to use.
Commercially available phosphines, Cp2ZrCl2 and Et3Al (Aldrich)
were used.
C(4)Hb, C(7)H2, C(6)H2, C(5)H2, C(8)H2), 1.39e1.47 (m, 2H, C(3)H,
C(2)Hа), 1.56e1.66 (m, 1H, C(2)Hb), 2.17e2.32 (m, 2H, C(1)H2),
7.40e7.55, 7.70e7.80 (m, 10H, Ph); MALDI TOF/TOF: [M
þ
H]þ
¼ 344.497, C22H31PO requires 343.457.
found
4.1.1.3. (3-Methyl-4-phenylbutyl)diphenylphosphine oxide (5b).
Yield 82%; Rf ¼ 0.37, white solid, mp ¼ 110e112 ꢀC. 31P NMR
4.1.1. The synthesis of substituted dialkyl-diphenylphosphine oxide
and deuterated analogs (general procedure)
(CDCl3):
d
33.02. 13C NMR (CDCl3): 18.96 (С(5)), 27.34 (1JC-P ¼ 72.0,
A round-bottomed flask in a dry argon atmosphere was charged
successively with stirring at
0
ꢀC with Cp2ZrCl2 (0.0584 g,
C(1)), 28.03 (C(2)), 35.91 (3JC-P ¼ 13.9, C(3)), 42.95 (С(4)), 125.83
(Ph), 128.20 (Ph), 128.64 (3JPh-P ¼ 11.5, Ph), 129.05 (Ph), 130.69,
130.72, 130.78 (Ph), 131.68 (Ph), 132.91 (1JC-P ¼ 98.1, Ph); 133.05
0.20 mmol), alkene (4 mmol), and AlEt3 (0.60 mL, 4 mmol). The
temperature was brought to ~20 ꢀC and the mixture was stirred for
8 h. Then toluene (10 mL) was added, the reaction mixture was
cooled to ꢁ5eꢁ10 ꢀС, dialkyl(diphenyl) chlorophosphine (4 mmol)
was added dropwise, and the mixture was stirred at room tem-
perature for an additional 6 h. Then the reaction mixture was
treated with a saturated aqueous solution of NH4Cl or D2O, the
reaction products were extracted with diethyl ether, and the sol-
vent was evaporated. Chloroform (10 mL) was added to the residue,
then 30% hydrogen peroxide (0.35 mL, 3 mmol) was slowly added
dropwise with vigorous stirring, and the mixture was stirred for
1 h. Then the reaction mixture was washed with water (3 ꢂ 5 mL)
and the organic phase was dried with MgSO4. The solvent was
evaporated and the residue was chromatographed on silica gel
(hexane: ethyl acetate: methanol ¼ 5:3:1).
(1JC-P ¼ 98.0, Ph), 140.66 (Ph).1H NMR (CDCl3):
d 0.84e1.01 (d, 3H,
(C(5)H3),1.62e1.90 (m, 3H, C(3)H, C(2)H2), 2.10e2.45 (m, 4Н, С(1)Н
2, С(4)Н2), 6.90e7.70, 7.70e7.80 (m, 15 H, Ph); MALDI TOF/TOF:
[M þ H]þfound ¼ 349.207, C23H25PO requires 348.417.
4.1.1.4. (2-Bicyclo[2.2.1]hept-2-ylethyl)diphenylphosphine oxide (5c).
Yield 79%; Rf ¼ 0.36, white solid, mp ¼ 108e110 ꢀC. 31P NMR
(CDCl3):
d
32.85. 13C NMR (CDCl3):
d
27.78 (2JСР ¼ 2.4, С(2)), 28.16
(1JС-Р ¼ 70.2, С(1)), 28.57 (C(6)), 29.85 (С(5)), 35.04 (С(9)), 36.38 (С
(7)), 37.69 (С(8)), 40.63 (С(4)), 43.42 (3JС-Р ¼ 14.4, С(3)), 128.50 (3JC-
¼ 11.5, Ph), 130.64 (2JC-P ¼ 9.2, Ph), 131.51 (4JСР ¼ 2.4, Ph), 133.03
P
(1JC-P ¼ 98.0, Ph), 133.06 (1JC-P ¼ 97.0, Ph). 1H NMR (CDCl3):
d
0.77e0.98 (m, 4H, (C(9)Hа, C(8)Hа, C(6)Hа, C(5)Hа), 1.01e1.09 (m,
1H, (C(8)Hb), 1.18e1.36 (m, 5Н, C(6)Hb, C(9)Hb, C(3)H, C(2)Hа,
С(5)Нb), 1.37e1.51 (m, 1H, C(2)Hb), 1.76e1.82 (m, 1Н, С(7)Н),
1.95e2.03 (m, 1Н, С(4)Н), 2.04e2.17 (m, 2H, C(1)H2), 7.20e7.40,
4.1.1.1. (3-Methylnonyl)diphenylphosphine oxide (5а). Yield 80%;
Rf ¼ 0.37, white solid, mp ¼ 59e61 ꢀC. 31P NMR (CDCl3):
d 33.28.
7.45e7.70 (m, 10H, Ph); MALDI TOF/TOF [M þ H]þ
¼ 325.307,
13C NMR (CDCl3):
d 14.10 (С(9)), 19.15 (С(10)), 22.64 (C(8)), 26.85
found
C
21H25PO requires 324.396.
(С(5)), 27.21 (1JC-P ¼ 72.4, С(1)), 28.05 (2JC-P ¼ 4.0, С(2)), 29.53
(С(6)), 31.85 (C(7)), 33.76 (3JC-P ¼ 14.1, С(3)), 36.28 (С(4)), 128.61
(3JC-P ¼ 11.1, Ph), 130.78 (2JC-P ¼ 9.05, Ph), 130.80 (2JC-P ¼ 9.05, Ph),
131.64 (4JC-P ¼ 3.0, Ph), 133.10 (1JC-P ¼ 97.6, Ph),133.20 (1JC-P ¼ 96.6,
4.1.1.5. (2-(3-Deuterobicyclo[2.2.1]hept-2-yl)ethyl)diphenylphos-
phine oxide (6c). Yield 76%; Rf
¼
0.36, white solid,
Ph). 1H NMR(CDCl3):
d 0.78e0.98 (m, 6H, (C(9)H3, C(10)H3),
mp ¼ 107e109 ꢀC. 31P NMR (CDCl3):
d
32.78. 13C NMR (CDCl3):
1.00e1.35 (m, 10H, (C(4)Hа, C(4)Hb, C(7)H2, C(6)H2, C(5)H2, C(8)
H2), 1.36e1.55 (m, 2H, C(3)H, C(2)Hа), 1.56e1.70 (м, 1H, C(2)Hb),
2.15e2.35 (m, 2H, C(1)H2), 7.40e7.58, 7.70e7.82 (m, 10H, Ph);
MALDI TOF/TOF: [M þ H]þfound ¼ 343.487, C22H31PO requires
342.455.
d
27.73 (2JС-Р ¼ 3.7, С(2)), 28.19 (1JС-Р ¼ 76.5, С(1)), 28.52 (C(6)),
29.85 (C(5)), 35.02 (C(9)), 36.28 (C(7)), 37.29 (t, JC-D ¼ 19.4, С(8)),
40.61 (C(4)), 43.32 (3JC-P ¼ 14.4, C(3)), 128.50 (3JC-P ¼ 11.5, Ph),
130.64 (2JC-P ¼ 9.2, Ph), 131.50 (4JC-P ¼ 2.7, Ph), 133.05 (1JC-P ¼ 97.7,
Ph), 133.07 (1JC-P ¼ 97.7, Ph). 1H NMR (CDCl3):
d 0.95e1.14 (m, 3H,
(C(9)Hа, C(6)Hа, C(5)Hа), 1.16e1.26 (m, 1H, C(9)Hb), 1.34e1.65 (m,
6Н, C(8)HD, C(3)H, C(2)Hb, C(6)Hb, С(5)Нb, C(2)Hа), 1.92e1.97 (m,
1Н, С(7)Н), 2.12e2.32 (m, 3Н, С(4)Н, C(1)H2), 7.42e7.56, 7.69e7.78
4.1.1.2. (3-Deuteromethylnonyl)diphenylphosphine
oxide
(6а).
Yield 78%; Rf ¼ 0.37, white solid, mp ¼ 58e60 ꢀC. 31P NMR (CDCl3):
d
33.19. 13C NMR (CDCl3):
d
14.14 (С(9)), 18.89 (t, JC-D ¼ 19.0, С(10)),
(m, 10H, Ph); MALDI TOF/TOF [M
C21H24DPO requires 325.398.
þ
H]þfound
¼
326.441,
22.67 (C(8)), 26.88 С((5)), 27.26 (1JC-P ¼ 72.5, С(1)), 28.07 (2JC-
¼ 4.0, С(2)), 29.57 (С(6)), 31.89 (C(7)), 33.71 (3JC-P ¼ 14.0, С(3)),
P
36.30 (С(4)), 128.65 (3JC-P ¼ 11.1, Ph), 130.81 (2JC-P ¼ 9.05, Ph),
4.1.1.6. (3-(2-Naphthyl)butyl)diphenylphosphine
oxide
(5d).
130.83 (2JC-P ¼ 9.05, Ph), 131.66 (4JC-P ¼ 3.0, Ph), 133.16 (1JC-P ¼ 97.6,
Yield 73%; Rf ¼ 0.37, white solid, mp ¼ 113e115 ꢀC. 31P NMR
Ph), 133.27 (1JC-P ¼ 97.7, Ph). 1H NMR(CDCl3):
d
0.80e0.87 (m, 5H,
(CDCl3):
d
32.89. 13C NMR (CDCl3): 22.54 (С(14)), 27.79 (1JC-P ¼ 72.4,
(C(9)H3, C(10)H2D), 1.04e1.14 (m, 1H, (C(4)Hа), 1.15e1.31 (m, 9Н,
C(1)), 29.33 (2JC-P ¼ 3.0, C(2)), 41.15 (3JC-P ¼ 14.1, C(3)), 125.44 (С(5)),

L.К. Dil'mukhametova et al. / Journal of Organometallic Chemistry 824 (2016) 73e79
77
125.58 (С(9)), 125.62 (С(7)), 126.07 (С(13)), 127. 65 (С(8)), 127.67
(С(12)),128.36 (С(10)), 128.66 (3JPh-P ¼ 12.1, Ph), 130.69 (2JC-P ¼ 10.1,
Ph), 130.87 (2JC-P ¼ 9.05, Ph), 131.72 (4JC-P ¼ 3.0, Ph), 131.74 (4JC-
(С(6)), 32.01 (C(7)), 32.96 (2JCP ¼ 16.1, С(2)), 34.12 (3JC-P ¼ 12.1,
С(3)), 36.61 (С(4)), 128.41, 128.54 (3JC-P ¼ 7.0, Ph), 132.70, 132.82
(2JC-P ¼ 18.1, Ph), 138.70, 138.82, 138.93, 138.98 (Ph). 1H NMR
¼ 2.0, Ph),132.42 (С(6)), 132.56 (1JC-P ¼ 97.5, Ph); 133.32 (1JC-
(CDCl3): d 0.78e0.98 (m, 6H, (C(9)H3, C(10)H3), 1.10e1.40 (m, 11H,
P
¼ 98.5, Ph), 133.62 (С(11)), 143.19 (С(4)). 1H NMR (CDCl3):
С(2)На, (C(4)Hа, C(4)Hb, C(7)H2, C(6)H2, C(5)H2, C(8)H2), 1.44e1.61
(m, 2H, C(3)H, C(2)Hb), 2.00e2.19 (m, 2H, C(1)H2), 7.40e7.58,
P
d
1.33e1.35 (d, 3H, (C(14)H3), 1.92e2.26 (m, 4H, C(2)H2, C(1)H2),
2.88e2.98 (m, 1Н, С(3)Н), 7.23e7.31, 7.34e7.97 (m, 17H, napht, Ph);
7.70e7.82 (m, 10H, Ph); MALDI TOF/TOF: [M þ H]þ
¼ 327.463,
found
MALDI TOF/TOF: [M þ H]þ
¼ 385.337, C26H25PO requires
C22H31P requires 326.455.
found
384.450.
4.1.2.2. (3-Methyl-4-phenylbutyl)diphenylphosphine
72%; colorless oil. 31P NMR (CDCl3): -15.72. 13C NMR (CDCl3): 19.28
d
(3b). Yield
4.1.1.7. (3-Cyclohexylbutyl)diphenylphosphine oxide (5e). Yield 84%;
Rf ¼ 0.39, white solid, mp ¼ 100e102 ꢀC. 31P NMR (CDCl3):
d
33.23.
(С(5)), 25.60 (2JC-P ¼ 9.05, C(2)), 32.76 (1JC-P ¼ 7.00, C(1)), 36.29
(3JC-P ¼ 10.1, C(3)), 43.23 (С(4)), 125.78 (Ph), 128.22, 128.43, 128.51,
129.23 (Ph); 132.73 (2JC-P ¼ 18.1, Ph), 132.87 (2JC-P ¼ 19.1, Ph),
138.91 (1JC-P ¼ 24.1, Ph); 139.01 (1JC-P ¼ 23.1, Ph), 141.21 (Ph)).1H
13C NMR (CDCl3): 15.65 (С(10)), 25.43 (2JC-P ¼ 4.0, C(2)), 26.63
(С(6)), 26.67 (С(8)), 26.78 С((7)), 27.66 (1JC-P ¼ 72.0, C(1)), 28.36
С((5)), 30.68 С((9)), 39.13 (3JC-P ¼ 13.8, C(3)), 42.07 С((4)), 128.60
(3JPh-P ¼ 11.5, Ph), 130.75 (2JC-P ¼ 9.1, Ph), 131.61 (4JC-P ¼ 2.3, Ph),
133.13 (1JC-P ¼ 97.7, Ph); 133.19 (1JC-P ¼ 97.8, Ph). 1H NMR (CDCl3):
NMR (CDCl3):
d 0.92e1.00 (d, 3H, (C(5)H3), 1.34e1.47 (m, 1H, (C(1)
Hа), 1.53e1.68 (m, 1H, C(1)Hb), 1.87e1.98 (m, 1H, C(3)H), 2.05e2.25
(m, 2H, C(2)H2), 2.38e2.46 (m, 1H, C(4)Ha), 2.66e2.76 (m, 1Н,
С(4)Нb), 7.10e7.65, 7.70e7.80 (m, 15 H, Ph); MALDI TOF/TOF: [M þ
H]þfound ¼ 333.221, C23H25P requires 332.418.
d
0.80e0.82 (d, 3H, (C(10)H3), 0.85e1.67 (m, 14H, C(5)Ha, C(9)Ha,
C(7)H2, C(4)H, C(3)H, C(2)H2, C(9)Hb, C(5)Hb, C(6)H2, C(8)H2)
2.14e2.29 (m, 2Н, С(1)Н2), 7.44e7.48, 7.70e7.75 (m, 10H, Ph);
MALDI TOF/TOF: [M þ H]þfound ¼ 341.611, C22H29PO requires
340.439.
4.1.2.3. (2-Bicyclo[2.2.1]hept-2-ylethyl)diphenylphosphine
(3c).
Yield 70%, colorless oil. 31P NMR (CDCl3): -15.55; 13C NMR (CDCl3):
d
4.1.1.8. (3-Methylnonyl)diethylphosphine oxide (5f). Yield 77%;
d
26.50 (1JС-Р ¼ 11.1, С(1)), 28.89 (C(6)), 30.15 (С(5)), 33.01 (2JС-
Rf ¼ 0.38, colorless oil. 31P NMR (CDCl3):
d
54.16. 13C NMR (CDCl3):
¼ 16.1, С(2)), 35.31 (С(9)), 36.62 С((7)), 38.15 (С(8)), 40.96 (С(4)),
Р
d
5.73 (2JC-P ¼ 5.0, C(12)), 5.75 (2JC-P ¼ 5.0, C(120)), 14.15 (С(9)), 19.11
43.86 (3JС-Р ¼ 12.1, С(3)), 128.40, 128.47 (Ph), 132.78 (2JC-P ¼ 18.1,
(C(10)), 19.88 (1JCP ¼ 63.7, C(11), C(110)), 22.62 (C(8)), 24.05 (1JC-
Ph),138.15,138.08,138.04,138.00 (Ph). 1H NMR (CDCl3):
d 1.03e1.40
¼ 65.3, С(1)), 26.87 (С(5)), 28.27 (2JC-P ¼ 4.0, С(2)), 29.53 (С(6)),
(m, 6H, (C(9)Hа, C(8)Hа, C(6)Hа, C(5)Hа, C(9)Hb, C(2)Hа), 1.46e1.62
(m, 5H, (C(8)Hb, C(2)Hb, С(5)Нb, C(6)Hb, C(3)H), 2.04e2.17 (m, 3Н,
С(4)Н, C(1)H2), 2.23e2.30 (m, 1Н, С(7)Н), 7.30e7.60, 7.80e7.98 (m,
P
31.83 (C(7)), 33.87 (3JC-P ¼ 13.1, С(3)), 36.35 С(4). 1H NMR (CDCl3):
d
0.87e0.95 (m, 6H, (C(9)H3, C(10)H3), 1.13e1.83 (m, 25H, (C(4)Hа,
C(12)H3, C(120)H3, C(7)H2, C(6)H2, C(5)H2, C(8)H2, C(4)Hb, C(2)Hb,
10H, Ph); MALDI TOF/TOF [M þ H]þ
¼ 309.312, C21H25P re-
found
C(3)H, C(2)Hа, C(1)H2, C(11)H2, C(110)H2); MALDI TOF/TOF [M þ
quires 308.397.
H]þ
¼ 247.596, C14H31PO requires 246.339.
found
4.1.2.4. (3-(2-Naphthyl)butyl)diphenylphosphine (3d). Yield 67%,
4.1.1.9. (3-Deuteromethylnonyl)diethylphosphine
oxide
d
(6f).
white solid, mp ¼ 109e111 ꢀC. 31P NMR (CDCl3):
d
-15.73; 13C NMR
Yield 74%; Rf ¼ 0.38, colorless oil. 31P NMR (CDCl3):
52.24. 13C
(CDCl3):
d
22.59 C(14)), 26.06 (1JС-Р ¼ 11.1, С(1)), 34.22 (2JС-Р ¼ 16.1,
NMR (CDCl3):
d
5.79 (2JC-P ¼ 5.2, C(12), (C(120)), 13.87 (С(9)), 18.63
С(2)), 41.43 (3JС-Р ¼ 12.1, С(3)), 125.30 (С(5)), 125.55 (С(9)), 125.88
(С(7)), 125.97 (С(13)), 127. 71 (С(8)), 128.17 (С(12)), 128.45 (Ph),
128.67 (С(10)), 132.41 (С(6)), 132.66 (2JС-P ¼ 18.1, Ph), 132.98 (2JС-
(t, JC-D ¼ 18.6, С(10)), 19.86 (1JC-P ¼ 66.2, C(11), C(110)), 22.43 (C(8)),
24.04 (1JC-P ¼ 65.1, С(1)), 26.68 (С(5)), 28.11 (2JC-P ¼ 4.0, С(2)),
29.34 (С(6)), 31.64 (C(7)), 33.63 (3JC-P ¼ 13.0, С(3)), 36.15 (С(4)).1H
¼ 18.5, Ph), 133.74 (С(11)), 138.44, 138.57, 139.02, 139.15 (Ph),
P
NMR (CDCl3):
d
0.75e0.85 (m, 5H, (C(9)H3, C(10)H2D), 1.00e1.73
144.19 (С(4)).1H NMR (CDCl3):
d
1.40e1.48 (d, 3H, (C(14)H3),
(m, 25H, (C(4)Hа, C(12)H3, C(120)H3, C(7)H2, C(6)H2, C(5)H2, C(8)
H2, C(4)Hb, C(2)Hb, C(3)H, C(2)Hа, C(1)H2, C(11)H2, C(110)H2);
MALDI TOF/TOF [M þ H]þfound ¼ 248.609, C14H31PO requires
247.371.
1.92e2.16 (m, 4H, (C(2)H2, C(1)H2), 3.06e3.13 (m, 1Н, С(3)Н),
7.37e7.62, 7.66e7.72, 7.88e7.97 (m, 17H, Ph, napht); MALDI TOF/
TOF [M þ H]þ
¼ 369.322, C26H25P requires 368.450.
found
4.1.2.5. (3-Cyclohexylbutyl)diphenylphosphine
(3e). Yield 68%;
d
-15.56. 13C NMR (CDCl3): 16.02
4.1.1.10. (2-(3-Deuterobycyclo[2.2.1]hept-2-yl)ethyl)dieth-
colorless oil. 31P NMR (CDCl3):
ylphosphine oxide (6g). Yield 72%; Rf ¼ 0.37, colorless oil. 31P NMR
(С(10)), 26.05 (2JC-P ¼ 11.1, C(1)), 26.87 (С(6)), 27.01 (С(8)), 26.93
С((7)), 28.60 С((5)), 30.34 (1JC-P ¼ 16.1, C(2)), 30.90 С((9)), 39.49
(3JC-P ¼ 12.3, C(3)), 42.30 С((4)), 128.45, 128.51(3JС-P ¼ 6.0, Ph),
132.75 (2JС-P ¼ 18.2, Ph), 132.85 (2JС-P ¼ 18.3, Ph),139.09, 139.22,
(CDCl3):
d
52.02. 13C NMR (CDCl3):
d
5.85 (2JC-P ¼ 4.7, C(11)), (C(110)),
20.17 (1JC-P ¼ 65.8, C(10), C(100)), 25.31 (1JC-P ¼ 64.8, С(1)), 28.16
(2JC-P ¼ 3.1, С(2)), 28.67 (С(6)), 30.03 (С(5)), 35.24 (C(9)), 36.47
(С(7)), 37.52 (t, JC-D ¼ 19.3, С(8)), 40.86 (С(4)), 43.65 (3JC-P ¼ 13.5,
139.33 (Ph). 1H NMR (CDCl3):
d 0.94e0.96 (d, 3H, (C(10)H3),
С(3)). 1H NMR (CDCl3):
d
1.07e1.22 (m, 9H, (C(9)Ha, C(5)Ha, C(6)Ha,
1.07e1.81 (m, 14H, C(5)H2, C(9)H2, C(7)H2, C(4)H, C(3)H, C(1)H2,
C(6)H2, C(8)H2) 2.07e2.20 (m, 2Н, С(2)Н2), 7.44e7.48, 7.70e7.75
C(11)H3, C(110)H3), 1.27e1.57 (m, 7H, C(9)Hb, C(2)H2, C(3)H, C(8)HD,
C(5)Hb, C(6)Hb), 1.63e1.77 (m, 6Н, С(1)Н2, С(10)Н2, С(100)H2),
1.95e2.00 (m, 1Н, С(4)Н), 2.18e2.23 (m, 1Н, C(7)Н); MALDI TOF/TOF
(m, 10H, Ph); MALDI TOF/TOF [M þ H]þ
¼ 325.601, C22H29
P
found
requires 324.439.
[M þ H]þ
¼ 230.543, C13H24DPO requires 229.313.
found
4.1.3. Synthesis of (3-methylnonyl)diphenylphosphine sulfide (7а)
4.1.2. Reduction of substituted phosphineoxides
Substituted phosphines 3a-c were prepared as described earlier
[27e30].
(3-Methylnonyl)diphenylphosphine sulfide 7a was prepared as
described earlier [27e30].
Yield 71%; Rf ¼ 0.37, yellow oil; 31P NMR (CDCl3):
d
43.44; 13C
NMR (CDCl3):
d 14.18 (С(9)), 19.38 (С(10)), 22.66 (C(8)), 26.83
4.1.2.1. (3-Methylnonyl)diphenylphosphine (3
а
). Yield 69%, colorless
(С(7)), 28.90 (2JC-P ¼ 2.0, С(2)), 29.53 (С(6)), 30.10 (1JC-P ¼ 45.5,
С(1)), 31.86 (C(7)), 33.45 (3JC-P ¼ 12.1, С(3)), 36.36 (С(4)), 128.59
(3JC-P ¼ 9.5, Ph), 131.04 (2JC-P ¼ 7.9, Ph), 131.05 (2JC-P ¼ 7.8, Ph),
oil. 31P NMR (CDCl3): -15.19. 13C NMR (CDCl3):
d d 14.22 (С(9)), 19.51
(С(10)), 22.77 (C(8)), 25.40 (1JC-P ¼ 10.05, С(1)), 27.01 (С(5)), 29.69

78
L.К. Dil'mukhametova et al. / Journal of Organometallic Chemistry 824 (2016) 73e79
131.35,131.37 (Ph),132.99 (1JC-P ¼ 63.5, Ph),133.07 (1JC-P ¼ 63.6, Ph).
C(81)Ha, C(91)Ha, C(21)Ha, C(61)Ha, C(91)Hb), 1.27e1.50 (m, 12H, C(3)
H, C(8)Hb, C(5)Ha, C(5)Hb, C(6)Hb, C(2)Hb, C(31)H, C(81)Hb, C(51)Ha,
C(51)Hb, C(61)Hb, C(21)Hb), 1.93e1.98 (m, 2H, C(7)H, C(71)H),
2.10e2.16 (m, 2H, C(4)H, C(41)H), 2.40e2.48 (m, 4H, C(1)H2, C(11)
H2), 7.39e7.50, 7.67e7.76 (m, 20H, Ph). Found: С, 63.58; H, 6.41.
1H NMR (CDCl3):
d 0.80e0.87 (m, 6H, (C(9)H3, C(10)H3), 1.00e1.30
(m, 10H, (C(4)Hа, C(4)Hb, C(7)H2, C(6)H2, C(5)H2, C(8)H2), 1.39e1.48
(m, 2H, C(3)H, C(2)Hа), 1.57e1.66 (m, 1H, C(2)Hb), 2.33e2.50 (m, 2H,
C(1)H2), 7.30e7.45, 7.76e7.86 (m, 10H, Ph); MALDI TOF/TOF [M þ
H]þ
¼ 359.501, C22H31PS requires 358.521.
C42H50P2PdCl2 requires С, 63.62; H, 6.35.
found
4.1.4. Synthesis of a Mo complex
Acknowledgments
Phosphine complexes of molybdenum 8 were prepared as pre-
viously described [30]. Then complexes 8 were purified by column
chromatography on silica gel (hexane as eluent).
This work was financially supported by the Russian Foundation
for Basic Research (Grants nos. 15-33-20043, 16-33-00310) and
Grants of RF President (MD-6293.2016.3, NSh-6651.2016.3). The
structural studies of the synthesized compounds were performed
with the use of Collective Usage Centre “Agidel” at the Institute of
Petrochemistry and Catalysis of RAS.
4.1.4.1. Complex Мо(СO)5L4a (8a). Yield 53%; Rf ¼ 0.40, dark blue
oil; 31P NMR (CDCl3): 27.79; 13C NMR (CDCl3):
d d 14.19 (С(9)), 19.08
(t, JC-D ¼ 19.0, С(10)), 22.72 (C(8)), 26.88 (С(5)), 29.56 (С(6)), 29.88
(1JC-P ¼ 22.0, С(1)), 30.73 (С(2)), 31.92 (C(7)), 33.94 (3JC-P ¼ 9.6,
С(3)), 36.43 (С(4)), 128.71 (d, 3JC-P ¼ 8.9, Ph), 129.97 (d, 3JC-P ¼ 8.2,
Ph), 131.86 (d, 2JC-P ¼ 11.4, Ph), 132.03 (d, 2JC-P ¼ 11.6, Ph), 136.83 (d,
1JC-P ¼ 34.6, Ph); 137.14 (d, 1JC-P ¼ 34.8, Ph), 205.85 (d, JC-P ¼ 8.7, CO),
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.2016.10.012.
210.22 (d, JC-P ¼ 22.3, CO);1H NMR (CDCl3):
d 0.89e1.01 (m, 5H,
(C(9)H3, C(10)H2D), 1.17e1.43 (m, 10H, (C(4)Hа, C(4)Hb, C(7)H2, C(6)
H2, C(5)H2, C(8)H2), 1.45e1.58 (m, 3H, C(2)H2, C(3)H), 2.36e2.54 (m,
2H, C(1)H2), 7.35e7.55, 7.60e7.66 (m, 10 H, Ph); IR (CHCl2, cmꢁ1),
References
[1] B.-B. Li, Y.-X. Jia, P.C. Zhu, R.J. Chew, Y. Li, N.S. Tan, P.-H. Leung, Eur. J. Med.
Chem. 98 (2015) 250e255, http://dx.doi.org/10.1016/j.ejmech.2015.05.027.
[2] M. Yamada, M. Yamashita, T. Suyama, J. Yamashita, K. Asai, T. Niimi, N. Ozaki,
M. Fujie, K. Maddali, S. Nakamura, K. Ohnishi, Bioorg. Med. Chem. Lett. 20
(2010) 5943e5946, http://dx.doi.org/10.1016/j.bmcl.2010.01.061.
[3] M. Yamashita, V.K. Reddy, L.N. Rao, B. Haritha, M. Maeda, K. Suzuki, H. Totsuka,
M. Takahashi, T. Oshikawa, Tetrahedron Lett. 44 (2003) 2339e2341, http://
dx.doi.org/10.1016/S0040-4039(03)00255-7.
[4] D.M. Cermak, D.F. Wiemer, K. Lewis, R.J. Hohl, Bioorg. Med. Chem. 8 (2000)
2729e2737, http://dx.doi.org/10.1016/S0968-0896(00)00212-1.
[5] A. Borner (Ed.), Phosphorus Ligands in Asymmetric Catalysis, Wiley-VCH,
Weinheim, 2008.
[6] Y. Wei, M. Shi, Acc. Chem. Res. 43 (2010) 1005e1018, http://dx.doi.org/
10.1021/ar900271g.
[7] Y. Xiao, Z. Sun, H. Guo, O. Kwon, Beilstein J. Org. Chem. 10 (2014) 2089e2121,
http://dx.doi.org/10.3762/bjoc.10.218.
[8] L. Kollar, G. Keglevich, Chem. Rev. 110 (2010) 4257e4302, http://dx.doi.org/
10.1021/cr900364c.
[9] B. Breit, E. Fuchs, Chem. Commun. (2004) 694e695, http://dx.doi.org/10.1039/
B315709A.
(
yCO): 2070 (s), 1987 (s). Found: С, 57.49; H, 5.40. C27H30DM
оО5P
requires: С, 57.55; H, 5.37.
4.1.4.2. Complex Мо(СO)5L3b (8b). Yield 44%; Rf ¼ 0.39, dark blue
oil; 31P NMR (CDCl3):
d
27.77; 13C NMR (CDCl3): 19.21 (С(5)), 30.09
(1JC-P ¼ 21.9, C(1)), 30.63 (2JC-P ¼ 2.4, C(2)), 36.34 (3JC-P ¼ 13.5,
C(3)), 43.22 (С(4)), 125.88, 128.24, 129.05, (Ph); 128.68, 128.70 (d,
3JC-P ¼ 9.05, Ph), 131.75 (d, 2JC-P ¼ 11.4, Ph), 131.96 (d, 2JC-P ¼ 11.5,
Ph), 136.57 (d, 1JC-P ¼ 33.5, Ph), 136.90 (d, 1JC-P ¼ 33.9, Ph), 140.61
(Ph)), 205.74 (d, JC-P ¼ 8.8, CO), 210.20 (d, JC-P ¼ 22.4, CO); 1H NMR
(CDCl3): d. 0.90e0.95 (d, 3H, C(5)H3), 1.19e1.32 (m, 1H, С(2)Ha),
1.42e1.54 (m, 1H, C(2)Hb),1.78e1.87 (m, 1H, C(3)H), 2.29e2.63 (m,
4H, C(1)H2, C(4)H2), 7.07e7.13, 7.19e7.32, 7.41e7.58 (m, 15H, Ph). IR
(CHCl2, cm-1), (yCO): 2070 (s), 1987 (s). Found: С, 59.10; H, 4.44.
C28H25МоО5P requires С, 59.17; H, 4.43.
[10] J. Klosin, C.R. Landis, Acc. Chem. Res. 40 (2007) 1251e1259, http://dx.doi.org/
10.1021/ar7001039.
[11] M. Sawamura, Y. Ito, Chem. Rev. 92 (1992) 857e871, http://dx.doi.org/
10.1021/cr00013a005.
[12] P.-H. Leung, Acc. Chem. Res. 37 (2004) 169e177, http://dx.doi.org/10.1021/
ar030008o.
[13] R.A. Baber, M.F. Haddow, A.J. Middleton, A.G. Orpen, P.G. Pringle, Organo-
metallics 26 (2007) 713e725, http://dx.doi.org/10.1021/om060912v.
[14] W. Tang, X. Zhang, Chem. Rev. 103 (2003) 3029e3070, http://dx.doi.org/
10.1021/cr020049i.
[15] T.P. Clark, C.R. Landis, Tetrahedron Asymmetry 15 (2004) 2123e2137, http://
dx.doi.org/10.1016/j.tetasy.2004.06.025.
[16] V.P. Ananikov, J.V. Ivanova, L.L. Khemchyan, I.P. Beletskaya, Eur. J. Org. Chem.
20 (2012) 3830e3840, http://dx.doi.org/10.1002/ejoc.201200342.
[17] J.L. Methot, W.R. Roush, Adv. Synth. Catal. 346 (2004) 1035e1050, http://
dx.doi.org/10.1002/adsc.200404087.
[18] I.R. Ramazanov, R.N. Kadikova, Z.R. Saitova, U.M. Dzhemilev, Asian J. Org.
Chem. 4 (11) (2015) 1301e1307, http://dx.doi.org/10.1002/ajoc.201500274.
[19] I.P. Beletskaya, M.A. Kazankova, Russ. J. Org. Chem. 38 (10) (2002) 1391e1430,
http://dx.doi.org/10.1023/A:1022685801622.
[20] K.M. Pietrusiewicz, M. Zablocka, Chem. Rev. 94 (1994) 1375e1411, http://
dx.doi.org/10.1021/cr00029a009.
[21] O. Delacroix, A.C. Gaumont, Curr. Org. Chem. 9 (2005) 1851e1882, http://
dx.doi.org/10.2174/138527205774913079.
[22] L. Coudray, J.-L. Montchamp, Eur. J. Org. Chem. (2008) 3601e3613, http://
dx.doi.org/10.1002/ejoc.200800331.
[23] I.P. Beletskaya, M.M. Kabachnik, Mendeleev Commun. 18 (2008) 113e120,
http://dx.doi.org/10.1016/j.mencom.2008.05.001.
[24] C.S. Demmer, N. Krogsgaard-Larsen, L. Bunch, Chem. Rev. 111 (2011)
7981e8006, http://dx.doi.org/10.1021/cr2002646.
[25] A.A. Zagidullin, I.A. Bezkishko, V.A. Miluykov, O.G. Sinyashin, Focus article,
Mendeleev Commun. 23 (2013) 117e130, http://dx.doi.org/10.1016/
j.mencom.2013.05.001.
[26] V.P. Ananikov, L.L. Khemchyan, Y.V. Ivanova, V.I. Bukhtiyarov, A.M. Sorokin,
I.P. Prosvirin, S.Z. Vatsadze, A.V. Medved’ko, V.N. Nuriev, A.D. Dilman,
4.1.4.3. Complex Мо(СO)5L3c (8c). Yield 49%; Rf ¼ 0.38, dark blue
oil; 31P NMR (CDCl3): 27.21; 13C NMR (CDCl3):
d d 28.70 (С(2)), 29.71
(C(6)), 29.96 (С(5)), 30.95 (d, 1JС-Р ¼ 21.5, С(1)), 35.14 (С(9)), 36.46
С((7)), 37.92 (С(8)), 40.78 (С(4)), 43.55 (d, 3JСР ¼ 13.1, С(3)), 128.63
(d, 3JC-P ¼ 9.2, Ph), 129.86 (Ph), 131.85 (d, 2JC-P ¼ 11.5, Ph), 136.86 (d,
1JCP ¼ 34.3, Ph), 136.92 (d, 1JC-P ¼ 34.3, Ph), 205.76 (d, JC-P ¼ 9.0, CO),
210.18 (d, JC-P ¼ 22.3, CO); 1H NMR (CDCl3):
d 0.92e1.21 (m, 5H,
(C(9)Hа, C(8)Hа, C(6)Hа, C(5)Hа, C(9)Hb), 1.25e1.52 (m, 5H, С(5)Нb,
C(6)Hb, C(8)Hb, C(2)H2), 1.93e1.98 (m, 1Н, С(4)Н), 2.11e2.15 (m, 1Н,
С(7)Н), 2.30e2.40 (m, 2H, C(1)H2), 7.40e7.60, 7.75e7.80 (m, 10H,
Ph); IR (CHCl2, cmꢁ1), (yCO): 2070 (s), 1987 (s). Found: С, 57.29; H,
4.90. C26H25МоО5P requires С, 57.36; H, 4.63.
4.1.5. Synthesis of a complex PdCl2L3c (9)
2
Reactions was performed under argon using standard Schlenk
techniques. A mixture of Pd(COD)Cl2 (0.79 g, 3 mmol) and
substituted phosphane 3c (3 mmol) was stirred under reflux in
6 mL CH2Cl2 for 5 h. The yellow solution became red during this
time. The solvent was removed under vacuum and the residue was
chromatographed on silica gel (hexane: ethyl acetate ¼ 7:1) to give
9 as yellow oil. Yield 41%; Rf ¼ 0.40; 31P NMR (MHz, CDCl3):
d 16.67;
13C NMR (CDCl3):
d
23.90 (d, 1JC-P ¼ 13.1, C(1)), 24.04 (d, 1JC-P ¼ 14.1,
C(11)), 28.79 (С(2)); 29.97 (С(6)), 30.94 (С(5)), 35.23 (С(9)), 36.53
3
((C(4)), 37.78 (C(8)), 40.80 (C(7)), 43.70 (d, JC-P ¼ 7.0, С(3)), 43.77
3
(d, JC-P ¼ 7.0, С(31)), 128.17, 130.30, 133.70, 133.73 (Ph). 1H NMR
(CDCl3): d 0.95e1.19 (m, 10H, C(8)Ha, C(9)Ha, C(2)Ha, C(6)Ha, C(9)Hb,

L.К. Dil'mukhametova et al. / Journal of Organometallic Chemistry 824 (2016) 73e79
79
V.V. Levin, I.V. Koptyug, K.V. Kovtunov, V.V. Zhivonitko, V.A. Likholobov,
A.V. Romanenko, P.A. Simonov, V.G. Nenajdenko, O.I. Shmatova,
V.M. Muzalevskiy, M.S. Nechaev, A.F. Asachenko, O.S. Morozov,
P.B. Dzhevakov, S.N. Osipov, D.V. Vorobyeva, M.A. Topchiy, M.A. Zotova,
S.A. Ponomarenko, O.V. Borshchev, Y.N. Luponosov, A.A. Rempel, A.A. Valeeva,
A.Y. Stakheev, O.V. Turova, I.S. Mashkovsky, S.V. Sysolyatin, V.V. Malykhin,
G.A. Bukhtiyarova, A.O. Terent’ev, I.B. Krylov, Russ. Chem. Rev. 83 (10) (2014)
885e985, http://dx.doi.org/10.1070/RC2014v083n10ABEH004471.
[27] V.A. D'yakonov, A.L. Makhamatkhanova, T.V. Tyumkina, U.M. Dzhemilev, Russ.
Chem. Bull. 61 (2012) 1556e1559, http://dx.doi.org/10.1007/s11172-012-
0205-4.
[31] V.A. D'yakonov, A.L. Makhamatkhanova, R.A. Agliullina, L.K. Dilmukhametova,
T.V. Tyumkina, U.M. Dzhemilev, Beilshtein J. Org. Chem. 12 (2016) 406e412,
http://dx.doi.org/10.3762/bjoc.12.43.
[32] U.M. Dzhemilev, A.G. Ibragimov, J. Organomet. Chem. 695 (2010) 1085e1088,
http://dx.doi.org/10.1016/j.jorganchem.2010.01.002.
[33] U.M. Dzhemilev, V.A. D'yakonov, Top. Organomet. Chem. 41 (2013) 215e244,
http://dx.doi.org/10.1007/3418_2012_38.
[34] C. Xi, S. Huo, T.H. Afifi, R. Hara, T. Takahashi, Tetrahedron Lett. 38 (1997)
4099e4102.
[35] S. Doherty, J.G. Knight, E.G. Robins, T.H. Scanlan, P.A. Champkin, W. Clegg,
J. Am, Chem. Soc. 123 (2001) 5110e5111, http://dx.doi.org/10.1021/
ja010090n.
[28] V.A.
D'yakonov,
A.L.
Makhamatkhanova,
L.K.
Dil'mukhametova,
T.V. Tyumkina, U.M. Dzhemilev, Russ. Chem. Bull. 62 (2013) 2467e2471,
http://dx.doi.org/10.1007/s11172-013-0357-x.
[29] V.A. D'yakonov, A.L. Makhamatkhanova, R.A. Kalimullina, T.V. Tyumkina,
U.M. Dzhemilev, Tetrahedron Lett. 55 (2014) 3913e3915, http://dx.doi.org/
10.1016/j.tetlet.2014.05.029.
[30] V.A. D'yakonov, A.L. Makhamatkhanova, L.K. Dil'mukhametova, R.A. Agliullina,
T.V. Tyumkina, U.M. Dzhemilev, Organometallics 34 (1) (2015) 221e228,
http://dx.doi.org/10.1021/om5010463.
[36] O. Kuhl, Phosphoros 31P NMR Spectroscopy: a Concise Introduction for the
Synthetic Organic and Organometallic Chemist, Springer-Verlag Berlin Hei-
delberg, 2008.
ꢀ
[37] K.W. Muir, F.Y. Petillon, R. Rumin, P. Schollhammer, J. Talarmin, J. Organomet.
Chem. 622 (2001) 297e301, http://dx.doi.org/10.1016/S0022-328X(00)
00874-3.
[38] G.M. Sheldrick, A short history of SHELX,, ActaCryst A64 (2008) 112e122,
http://dx.doi.org/10.1107/S0108767307043930.