Change of the coordination type for the phospholyl ligand under nucleophilic attack of H2O on phosphorus atom in 2,5- diphenylphosphacymantrene promoted by aliphatic amines

Article abstract of DOI:10.1016/j.ica.2011.01.094

η⁵-2,5-Diphenylphosphacymantrene (1) in benzene or CH ₂Cl₂ solution does not react with amines. However, with amines NHEt₂, NEt₃, NEt(i-Pr)₂ in excess and in the presence of small amounts of water 1 reacts to form anionic complexes [(CO)₃Mn(η⁴-Ph₂H₂C ₄P(O)H]^- A⁺, where cation A=H₂NEt2+ (2a), HNEt3+ (2b), HN(Et)(Prⁱ)2+ (2c). Probably, first an unstable intermediate with - bond is formed as a result of the attack by the activated H₂O molecule at the P atom. Afterwards, the rapid rearrangement occurs with migration of H from O to P which leads to the ligand 2,5-diphenyl-1 - phosphol-1-oxide, Ph₂H₂C₄P(O)H. Salts 2- have been characterized by ¹H, ³¹P, ¹³C NMR- and IR-spectra and the structures of 2a and 2c established by single crystal X-ray diffraction analyses. The phosphoryl ligand in anions 2a and 2c has the "envelope" conformation and is η⁴-coordinated with Mn(CO)₃. The phosphorus atom is not involved in the coordination with Mn because the Mn-P distances (2.7670(4) and 2.7732(8) ) are greater than the sum of covalent radii of P and Mn.

Full text of DOI:10.1016/j.ica.2011.01.094

Inorganica Chimica Acta 370 (2011) 292–296
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Change of the coordination type for the phospholyl ligand under nucleophilic
attack of H2O on phosphorus atom in 2,5-diphenylphosphacymantrene promoted
by aliphatic amines
⇑
Allan G. Ginzburg , Vasily V. Bashilov, Fedor M. Dolgushin, Alexander F. Smol’yakov, Pavel V. Petrovskii,
Viatcheslav I. Sokolov
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28, Vavilov St., 119991 Moscow, Russian Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 27 April 2010
Received in revised form 21 January 2011
Accepted 24 January 2011
Available online 3 February 2011
g
5-2,5-Diphenylphosphacymantrene (1) in benzene or CH2Cl2 solution does not react with amines. How-
ever, with amines NHEt2, NEt3, NEt(i-Pr)2 in excess and in the presence of small amounts of water 1 reacts
þ
þ
to form anionic complexes [(CO)3Mn(
g
4-Ph2H2C4P(@O)H]ꢀ A+, where cation A ¼ H2NEt2 (2a), HNEt3
(2b), HNðEtÞðPriÞ2 (2c). Probably, first an unstable intermediate with P–OH bond is formed as a result
of the attack by the activated H2O molecule at the P atom. Afterwards, the rapid rearrangement occurs
with migration of H from O to P which leads to the ligand 2,5-diphenyl-1-H-phosphol-1-oxide,
Ph2H2C4P(@O)H. Salts 2a–c have been characterized by 1H, 31P, 13C NMR- and IR-spectra and the struc-
tures of 2a and 2c established by single crystal X-ray diffraction analyses. The phosphoryl ligand in anions
þ
Keywords:
Manganese complexes
Phosphacymantrenes
Aliphatic amines
Nucleophilic addition
Phosphoryl rearrangement
X-ray crystal structures
2a and 2c has the ‘‘envelope’’ conformation and is
not involved in the coordination with Mn because the Mn–P distances (2.7670(4) and 2.7732(8) Å) are
greater than the sum of covalent radii of P and Mn.
g
4-coordinated with Mn(CO)3. The phosphorus atom is
Ó 2011 Elsevier B.V. All rights reserved.
1. Introduction
Ph or tert-Bu to P atom. Unstable anionic g
4-intermediates were
proposed for these reactions wherein the phospholyl ligand was
bonded to Mn(CO)3 through the diene system only; however, these
species were not isolated [10,11]. Early it was supposed that the
phospholyl ligand can be considered as a combination of two ‘‘sub-
The chemistry of the transition metal phospholyl complexes
including Fe, Mn, Rh and Co [1–3] has been intensely investigated
in recent years (see reviews [4–7]). Among other
complexes, the derivatives of manganese, phosphacymantrenes
-C4R4P)Mn(CO)3 where R = H, Alk, Ph have been studied in more
g
5-phospholyl
units’’, namely, the planar
atom P which could be coordinated separately or as a part of the
whole ligand (in
5-phospholyl complexes) [12].
g l-phosphido
4-diene fragment and
(g
details. A P(III) atom and CH group are isolobal and the former can
g
replace the latter in the Cp-ring until the complete replacement to
Previously, we found the novel reaction of solvopalladation of
5-2,5-diphenyl-phosphacymantrene (1) by means of Na2PdCl4
ꢀ
form cyclo-P5 [6,7]. Ligands C5R5 and C4R4P are isolobal but not
g
identical. In the properties of their manganese
g
5-complexes there
and NaOAc in alcoholic solutions (MeOH or EtOH). In this reaction,
the binuclear complexes with Pd2Cl2 core which contain groups
R = OMe or OEt bonded to phosphorus were formed [13]. In an at-
tempt to use new nucleophiles in the reactions of complex 1 we
studied its interaction with aliphatic amines under various condi-
tions (see preliminary communication [14]).
are both analogies (electrophilic substitution in the phospholyl
ring [8], exchange of CO ligands for phosphines) and differences
(unlike cymantrene, for example, 3,4-dimethylphosphacymant-
rene is not metallated with BuLi in THF). Quantum-chemical
calculations showed that in phosphacymantrenes LUMO is the
anti-bonding combination of pz (P) and dxz (Mn) orbitals which is
localized on the phosphorus atom [9,10]. Therefore one can expect
that the nucleophilic attack will be directed to P atom.
In this paper, we report on the preparation of the first stable
manganese anionic complexes with the ligand
g
4-2,5-diphenyl-
1-H-phosphol-1-oxide via the reaction of 1 with water and excess
Mathey et al. found that 3,4-dimethylphosphacymantrene re-
of aliphatic amines.
acted with PhLi or ButLi to give the products of the addition of
2. Results and discussion
⇑
Corresponding author. Fax: +7 499 135 5085.
E-mail addresses: allan@ineos.ac.ru (A.G. Ginzburg), sokol@ineos.ac.ru (V.I.
Reactions of 1 with amines were not studied before. We have
found that in benzene or CH2Cl2 1 does not react with aliphatic
Sokolov).
0020-1693/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2011.01.094

A.G. Ginzburg et al. / Inorganica Chimica Acta 370 (2011) 292–296
293
amines. However, if water is added and diethylamine or aliphatic
tertiary amines with rather high basicity (triethylamine or ethyldi-
isopropylamine) are in excess, 1 adds OHꢀ to the phosphorus atom
line solids, stable on keeping in inert atmosphere at 0 °C, the most
stable being 2c and the least stable 2a, respectively. Complexes 2a–
c have been characterized by 1H, 13C, 31P NMR and IR spectra. In
1H–{31P} NMR spectra signals of H–P protons are observed as broad
to give complexes 2a–c of the general formula [(OC)3Mn-g
4-2,5-
Ph2H2C4P(@O)H]ꢀ [HNR3]+, where NR3 = NHEt2 (2a), NEt3 (2b),
N(Et)(i-Pr)2 (2c) (Scheme 1). The crystalline products precipitate
gradually for 1–2 days at ambient temperature. Under these condi-
tions, the reaction has not gone to completion as shown by 31P
NMR since in the spectra of mother liquid signals both from start-
ing 1 (singlet at d ꢀ30.6 ppm) and of products 2a–c (downfield
shifted doublets centered at d ꢀ5 to ꢀ9 ppm with a characteristic
large coupling constant 1J(P–H) 536–549 Hz) were present. Under
these conditions, 1 does not react with either NH3 (gas) or a pri-
mary amine Ph2CH–NH2. According to 31P NMR when 2a dissolves
in DMSO it converts to starting 1.
singlets around d 7.8 ppm. In IR spectra, both
Mn(CO)3 undergo low-frequency shift by
= 45–60 cmꢀ1 that is
connected with the transfer from neutral molecule 1 to anionic
m(CO) bands of
D
m
complexes 2a–c. For 1 m
(CO) are 1955 cmꢀ1 (broad, E-mode) and
2025 cmꢀ1 (narrow, A1-mode), for 2a–c 1880–1890 cmꢀ1 (E) and
1980–1985 cmꢀ1 (A1), respectively. Interrelation of the linewidths
on the half-height of peaks characteristic of the Mn(CO)3 fragment
is retained. The structures of 2a and 2c have been established by
single crystal X-ray diffraction.
The cation and the anion in 2a occupy a general position. The
structure of complex anion 2a is presented in Fig. 1; the main geo-
metric parameters are given in Table 1. In the anion 2a heterocyclic
fragment has the ‘‘envelope’’ conformation. The carbon moiety
Thus the novel reaction has been observed wherein the role of
diethylamine and other amines apparently is to activate a water
molecule (probably through the formation of a hydrogen bond).
The formation of anionic complexes 2a–c probably begins with
the nucleophilic attack on the phosphorus atom by the H2O mole-
cule to primarily give a very unstable intermediate with fragment
P–OH followed by fast rearrangement with the migration of H from
O to P resulting in the final products 2a–c with a phosphoryl frag-
ment P(@O)H. Similar rearrangements are known in classical orga-
nophosphorus chemistry [15,16].
C(1)–C(4) is planar but the phosphorus atom P(1) is going out of
0
the carbon mean plane by 0.622 ÅA at the opposite side from the
manganese atom. The folding angle around C(1)–C(4) axis (the
dihedral angle
a between planes C(1)C(2)C(3)C(4) and C(1)–P–
C(4)) is 29.9°. The phosphorus atom has the distorted tetrahedral
environment of atoms C(1) and C(4) of the five-membered ring,
O(P) and H(P) atoms. It is not involved in the coordination with
Mn. The manganese atom is
g
4-coordinated with four carbon
Complexes 2a–c have the same anion [(CO)3Mn-
g
4-2,5-
atoms C(1)–C(2)–C(3)–C(4) only. The distance Mn(1)–P(1)
0
Ph2C4H2P(@O)H]ꢀ and different cations HNR3þ. They are crystal-
2.7670(4) ÅA in the anion 2a is greater than the sum of covalent ra-
Scheme 1.
Fig. 1. Structure of anion 2a. Thermal ellipsoids are drawn at 50% probability level.

294
A.G. Ginzburg et al. / Inorganica Chimica Acta 370 (2011) 292–296
Table 1
pendent molecules. Two anions have the identical structures close
Selected bond lengths (Å) and angles (°).
to that in 2a. Distances Mn(1)–P(1) are equal to 2.7732(8) and
0
2.7773(8) AÅ. The atom of0 P is going out of the carbon plane
C(1)C(2)C(3)C(4) by 0.611 ÅA in molecule A and 0.626 ÅA in molecule
Anion 2a
Anion 2c, molecule
A
Anion 2c, molecule
B
0
B, the dihedral angles
respectively. The oxygen atom P@O in the crystal 2c involved in
a of the ‘‘envelope’’ are 29.1° and 30.2°,
Mn(1)–C(1)
Mn(1)–C(2)
Mn(1)–C(3)
Mn(1)–C(4)
Mn(1)–C(5)
Mn(1)–C(6)
Mn(1)–C(7)
Mn(1)–P(1)
P(1)–C(1)
P(1)–C(4)
P(1)–O(1)
P(1)–H(1P)
C(1)–C(2)
C(2)–C(3)
2.1733(14) 2.170(3)
2.0859(14) 2.087(3)
2.0872(14) 2.080(3)
2.1603(14) 2.161(3)
1.7996(16) 1.789(3)
1.7978(16) 1.795(3)
1.7839(16) 1.787(3)
2.160(3)
2.087(3)
2.079(3)
2.177(3)
1.781(4)
1.799(4)
1.788(3)
2.7773(8)
1.770(3)
1.764(3)
1.506(2)
1.26(3)
1.443(4)
1.415(4)
1.445(4)
90.32(13)
112.0(2)
107.4(2)
107.16(19)
112.4(2)
106.8(13)
the formation of a strong hydrogen bond with one H atom
H(1NS) of the cation (i-Pr)2(Et)(H)N+. In this case, elongation of
0
the bond P@O (1.505 ÅA) is not significant comparing to Ph3PO,
probably because of one hydrogen bond involved unlike two bonds
for 2a.
The geometric parameters of
tially from those of the geometry of
2.7670(4)
2.7732(8)
1.7710(15) 1.775(3)
1.7683(15) 1.770(3)
1.5224(11) 1.5053(19)
g
4-anions 2a and 2c differ essen-
g
5-phosphacymantrenes. In
the structurally characterized
g
5-phosphacymantrene derivatives
1.268(17)
1.452(2)
1.412(2)
1.439(2)
90.47(7)
1.29(3)
0
1.439(4)
1.414(4)
1.430(4)
89.59(12)
the Mn–P bond distance is 2.332–2.390 ÅA that is less than the
sum of covalent radii, the phospholyl ligand is only slightly folded
around the C(1)–C(4) axis, the phosphorus atom is going out of the
plane C(1)–C(4) by no more than ꢁ0.05 Å [8,19–22]. For example,
in 3,4-dimethyl-2-benzoylphosphacymantrene the dihedral angle
C(3)–C(4)
C(1)–P(1)–C(4)
C(1)–C(2)–C(3)
C(3)–C(4)–P(1)
C(2)–C(1)–P(1)
C(4)–C(3)–C(2)
O(1P)–P(1)–
H(1P)
112.25(13) 112.5(2)
107.24(11) 108.48(19)
106.94(11) 107.43(19)
112.51(13) 111.8(2)
a
is 2.15°, the carbon moiety is planar and the phosphorus atom
is going out of the carbon mean plane by 0.048(2) Å [8]. In binu-
107.1(8)
105.9(13)
clear complexes with the Pd2Cl2 core Mn–P bond lengths are great-
0
er (2.447(2)–2.475(2) ÅA) and close to the sum of the covalent radii
of Mn and P, folding angle
a is near to 2.5° and phosphorus atom is
going out of the C(1)–C(4) plane away from the Mn atom by
dii (rMn = 1.35–1.39 Å, rP = 1.07–1.13 Å) [17,18]. The strong elonga-
tion of the distance Mn(1)–P(1) and the large dihedral angle of
‘‘envelope’’ folding permits us to make the conclusion that the
bond Mn–P in 2a is absent. The anions 2a–c have 18-electron con-
figuration (electron count: 4e C(1)–C(4), 6e 3CO, 7e Mn and 1e neg-
ative charge).
The length of the P@O bond, 1.522(1) Å0 in 2a, is greater than
that in triphenylphosphine oxide (1.484 ÅA). The oxygen atom
O(1P) in anion 2a is involved in two strong H-bonds with H(1NA)
and H(1NB) with the formation of the H-bonded centrosymmetric
dimers (Fig. 2). This may be the reason for some elongation of the
P@O bond.
0.055 Å [13].
a
Two related
g
4-zwitterionic complexes (CO)3Mnꢀ-[
g
4-3,4-
Me2C4H2P+(Ph)CH2CH2CO2Et [10] and (CO)3Mnꢀ-[
g
4-1,2,3,4-(CO2-
Me)4C4P+Me2] [23] for which the same structural characteristics
were observed were reported previously. The non-bonding dis-
tances Mn–P are 2.765 [10] and 2.828 Å [23], the phosphorus atom
is going out of the plane C(1)–C(4) by 0.66 and 0.64 Å, respectively.
It is worth to note that the bonds Mn(1)–C(2) and Mn(1)–C(3) are
shorter, than Mn(1)–C(1) and Mn(1)–C(4) bonds for all
g
4-com-
plexes. Perhaps, these differences can be connected with the pres-
ence of two substituents at the phosphorus atom. The orientation
of Mn(CO)3 in all
cated under the P atom, in the trans-position to the (C2)–(C3) bond.
g
4-complexes is such that one carbonyl group is lo-
The X-ray crystallographic study of 2c (Fig. 3 and Table 1)
showed that in an unit cell there are two crystallographically inde-
Fig. 2. H-bonded centrosymmetric dimers in crystal 2a (N(1S). . .O(1P) 2.804(7) Å, N(1S)–H(1NA). . .O(1P) 165°; N(1S). . .O(1PA)ꢀx+2,ꢀy+1,ꢀz 2.751(7) Å, N(1S)–
H(1NB). . .O(1PA)ꢀx+2,ꢀy+1,ꢀz 162°).

A.G. Ginzburg et al. / Inorganica Chimica Acta 370 (2011) 292–296
295
Fig. 3. Structure for anion 2c. For two independent molecules the N(1S). . .O(1P) distances are 2.713(3) and 2.669(3) Å, and the N(1S)–H(1NS). . .O(1P) angles are 162 and 170°.
Probably, the steric hindrance of the bulky phosphoryl fragment
causes the change in the geometry of
4-anionic complex as com-
paring with on the
5-neutral compounds, namely, large angle
161.9 MHz for 31P and 100.6 MHz for 13C). The chemical shifts were
measured relative to H3PO4
31P) and TMS (1H, 13C). All complexes
were obtained and handled in argon atmosphere.
g
(
g
a
‘‘envelope’’ folding around the axis C(1)–C(4) and the significant
exit of the P atom out of plane to the side opposite to the Mn atom.
Consequently, the distance P–Mn becomes too lengthy for bonding
and the change of hapticity occurs: from hapto-5 in starting 1 to
hapto-4 in final 2.
4.2. Synthesis of the complexes 2a–c
Complexes 2a–c were obtained by the standard procedure: un-
der inert atmosphere to 30–37.4 mg (0.08–0.1 mmol) of 1 in 3–
4 ml of benzene was added 0.5–0.8 ml of the corresponding amine
and 1–2 drops of water. After mixing and storage in the dark for 1–
2 days yellow-gray crystals of 2a–c precipitated. The solution was
decanted, and 6–8 ml of pentane was added. The crystals formed
were washed with pentane and dried in vacuo.
Complex 2a: From 30.1 mg (0.08 mmol) 1 and 0.6 ml of NHEt2
was obtained 20 mg (54%) 2a. Anal. Calc. for C23H25MnNO4P: C,
59.36; H, 5.41; N, 3.01. Found: C, 59.13; H, 5.45; N, 3.16%. 1H–
3. Conclusions
The new reaction of 2,5-diphenylphosphacymantrene with
water and the aliphatic amines has been found. As a result of the
cooperative process involving the nucleophilic attack of H2O on
the P atom followed by the migration of one H atom from H2O to
phosphorus atom and another one to amine, the
gand 2,5-diphenyl-1-H-phosphol-1-oxide coordinated to Mn is
g
4-phosphoryl li-
{
31P}NMR (DMSO-d6): d, ppm: 7.83 (s, 1H, P–H); 7.31, 7.20, 7.01,
10H, o, m, p C6H5; 5.52 (d, 2H, 3J(H3,4–P) = 12.7 Hz); 2.81 (k, 4H,
N–CH2, J(H–H) = 7.0 Hz); 1.09 (t, J(H–H) = 7.0 Hz, 6H, CH3); from
1H NMR-spectra 1J(P–H) = 549 Hz. 31P NMR (CD2Cl2): d ꢀ8.70 (dt,
þ
þ
formed. Salts 2a–c with the cations H2NEt2
,
HNEt3 ,
HNðEtÞðPriÞ2 have been prepared for the first time and character-
ized by 1H, 31P, 13C NMR and IR-spectra, and the structures of 2a
and 2c being established by the single crystal X-ray diffraction
analysis.
þ
1J(P–H) = 549, 3J(P–H3,4) = 12.7 Hz. IR-spectra (CH2Cl2):
m(CO)
1895 cmꢀ1 (broad, E-mode), 1980 cmꢀ1 (A1-mode).
Complex 2b: From 37.4 mg (0.1 mmol) 1 and 0.8 ml of NEt3 was
obtained 25 mg (51%) of 2b. Anal. Calc. for C25H29MnNO4P: C,
60.86; H, 5.92; N, 2.84. Found: C, 60.83; H, 5.94; N, 2.78%.
1H{31P}NMR(CD2Cl2), d ppm: 7.98 (broad s, 1H, P–H); 7.36,7.32,
7.24, 10H, o, m, p C6H5; 5.45, d, 2H, 3J(H3,4–P) = 14 Hz, H(3,4);
2.60, 6H, N–CH2; 1.02, 9H, CH3. 31P NMR (CD2Cl2): d ꢀ5.11 (dt,
1J(P–H) = 540 and 3J(P–H3.4) = 14Hz). 13C NMR (CD2Cl2): d 229.04,
Mn(CO)3; 139.54, key C-atoms of C6H5; 128.65, 125.23, 124.70,
C-atoms of m, o, p-positions of C6H5; 78.95, d, J(13C–31P) = 14 Hz,
4. Experimental
4.1. General
2,5-Diphenylphosphacymantrene (1) was prepared according to
the procedure [24]. 1H, 31P and 13C NMR spectra were recorded
using spectrometer Bruker Avance-400 at 400.16 MHz for 1H,

296
A.G. Ginzburg et al. / Inorganica Chimica Acta 370 (2011) 292–296
Table 2
absorption correction, and SHELXTL [26] for space group and struc-
ture determination, refinements, graphics, and structure reporting.
The structures were solved by direct methods and refined by the
full matrix least-squares technique against F2 with the anisotropic
thermal parameters for all non-hydrogen atoms. In the crystal 2c in
independent part molecule A, one of the two independent cations
(HNðEtÞðPriÞ2þ) is disordered over two positions with 0.75/0.25
occupancies. The hydrogen atoms at the N and P atoms in two
compounds 2a and 2c were localized from different Fourier syn-
thesis and involved in refining in isotropic approximation. All other
hydrogen atoms of 2a and 2c were placed geometrically and re-
fined in the riding motion approximation. The principal experi-
mental and crystallographic parameters of 2a and 2c are
presented in Table 2.
Crystal data, data collection and structure refinement parameters for 2a and 2c.
Complex
2a
2c
Formula
(C19H13MnO4P)ꢀ(C4H12N)+ (C19H13MnO4P)ꢀ(C8H20N)+
465.35
0.30 ꢂ 0.13 ꢂ 0.12
monoclinic
P21/n
Formula weight
Dimension (mm)
Crystal system
Space group
Unit cell dimensions
a (Å)
521.45
0.35 ꢂ 0.28 ꢂ 0.15
monoclinic
P21/c
10.6877(4)
11.0570(5)
19.2435(8)
90.00
94.6210(10)
90.00
2266.69
4
1.364
12.076(7)
12.387(7)
34.9402(19)
90.00
93.360(10)
90.00
5217.6
8
1.328
b (Å)
c (Å)
a
(°)
b (°)
c
(°)
V (Å3)
Z
qcalc (g cmꢀ3
)
Acknowledgements
Linear absorption
6.81
6.00
(l
) (cmꢀ1
)
This work has been done under financial support of the Russian
Foundation for Basic Research (Projects 08-03-00169, 11-03-00262
and 08-03-00631).
Tmin/Tmax
2hmax (°)
No. unique refl.
(Rint
No. observed refl.
(I > 2 (I))
0.821/0.925
58
6008(0.0304)
0.81/0.908
54
11,326(0.0531)
)
4985
8378
Appendix A. Supplementary material
r
No. parameters
285
677
R1 (on F for
0.0323
0.0513
CCDC 764036 and 764037 contains the supplementary crystal-
lographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associ-
ated with this article can be found, in the online version, at
doi:10.1016/j.ica.2011.01.094.
observed refl.)a
wR2 (on F2 for all
refl.)b
0.0828
1.036
0.1184
1.014
Goodness-of-fit
(GOF)on F2
P
P
a
R1
=
||Fo| ꢀ |Fc||/ |Fo|.
ꢄ
ꢂ
ꢃ
ꢅ
1
ꢀ
ꢁ
2
P
P
2
F2o ꢀ F2c
=
wðF2oÞ
.
b
wR2
¼
w
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[2] D. Carmichael, L. Ricard, N. Seeboth, Organometallics 26 (2007) 2964.
[3] Y. Cabon, D. Carmichael, K. Forissier, F. Mathey, L. Ricard, N. Seeboth,
Organometallics 26 (2007) 5468.
atoms in
(CH2Cl2):
a
m
-positions to P; 45.70, N–CH2; 9.11, CH3. IR-spectra
(CO) 1890 (E-mode), 1980 cmꢀ1 (A1-mode).IR-spectra
in solid state (Nujol): 1870 (E-mode), 1965 cmꢀ1 (A1-mode).
Complex 2c: From 37.4 mg (0.1 mmol) 1 and 0.8 ml of N(Et)(i-
Pr)2 was obtained 35 mg (66%) of 2c. Anal. Calc. for C27H33MnNPO4:
C, 62.19; H, 6.38; N, 2.69. Found: C, 62.21; H, 6.38; N, 2.61%.
1H{31P}NMR (CD2Cl2), d ppm: 7.94, broad s, 1H, P–H; 7.38, 7.23,
7.06, 10H, o, m, p C6H5; 5.44, d, 2H, 3J(H3,4–P) = 14 Hz, H(3,4);
3.18, 2H, N–CH; 2.69, 2H, N–CH2; 1.10, broad s, 15H, all Me-groups.
[4] F. Mathey, J. Organomet. Chem. 646 (2002) 15.
[5] D. Carmichael, F. Mathey, Top. Curr. Chem. 220 (2002) 27.
[6] F. Mathey, Angew. Chem., Int. Ed. 42 (2003) 1578.
[7] A.G. Ginzburg, Usp. Khim. 78 (3) (2009) 211 (Russ. Chem. Rev. 78 (3) (2009)
211).
[8] F. Mathey, A. Mitschler, R. Weiss, J. Am. Chem. Soc. 100 (1978) 5748.
[9] C. Guimon, G. Pfister-Guilloso, F. Mathey, Nouv. J. Chim. 3 (1979) 725.
[10] B. Deschamp, P. Toullec, L. Ricard, F. Mathey, J. Organomet. Chem. 634 (2001)
131.
[11] B. Deschamp, L. Ricard, F. Mathey, J. Organomet. Chem. 689 (2004) 4647.
[12] L. Brunet, F. Mercier, L. Ricard, F. Mathey, Angew. Chem., Int. Ed. 33 (1994) 742.
[13] A.G. Ginzburg, V.V. Bashilov, F.M. Dolgushin, A.F. Smol’yakov, A.S. Peregudov,
V.I. Sokolov, J. Organomet. Chem. 694 (2009) 72.
[14] V.V. Bashilov, A.G. Ginzburg, A.F. Smol’yakov, F.M. Dolgushin, P.V. Petrovskii,
V.I. Sokolov, Izv. Akad. Nauk Ser. Khim. (2010) 476 (Russ. Chem. Bull., Int. Ed.
59 (2010) 486).
31P NMR (CD2Cl2):
d
ꢀ4.95 (dt, 1J(P–H) = 536 and 3J(P–
H
3.4) = 14 Hz). 13C NMR (CD2Cl2): d 228.26, Mn(CO)3; 139.94, key
C-atoms of C6H5; 128.49, 125.31 and 125.25, 124.52, C-atoms of
m-, two types of o-, p-positions C6H5; 79.13,d, J(13C–31P) = 21 Hz,
two C-atoms in b-positions to P; 65.10, d, J(13C–31P) = 87 Hz, two
C-atoms in
CH. IR (CH2Cl2):
a-positions to P; 41.69, N–CH2; 17.72, CH3; 12.36, N–
[15] A. Michaelis, L. Gleichmann, Chem. Ber. 15 (1882) 801.
[16] A. Kirby, S.D. Warren, The Organic Chemistry of Phosphorus, Elsevier,
Amsterdam, London, New York, 1967.
[17] S.S. Batsanov, Zh. Neorg. Chim. 36 (1991) 3015 (Russ. J. Inorg. Chem. 36 (1991)
1694).
m
(CO) 1890 (E-mode) and 1980 cmꢀ1 (A1-mode).
IR-spectra in solid state (Nujol): 1885 (E-mode), 1970 cmꢀ1 (A1-
mode).
[18] B. Cordero, V. Gomez, A.E. Platero-Prats, M. Reves, J. Echeverria, E. Cremades, F.
Barragan, S. Alvares, J. Chem. Soc., Dalton Trans. (2008) 2832.
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(1991) 417.
[20] P. Toullec, L. Ricard, F. Mathey, Organometallics 22 (2003) 1340.
[21] P. Toullec, L. Ricard, F. Mathey, Organometallics 21 (2002) 2635.
[22] A. Decken, F. Bottomley, B.E. Wilkins, E.D. Gill, Organometallics 23 (2004)
3683.
[23] E. Linder, A. Rau, S. Hoehne, J. Organomet. Chem. 218 (1981) 41.
[24] A. Breque, F. Mathey, C. Santini, J. Organomet. Chem. 165 (1979) 129.
[25] APEX II Software Package, Bruker AXS Inc., 5465, East Cheryl Parkway, Madison,
WI 5317, 2005.
[26] SHELXTL v. 5.10, Structure Determination Software Suite, Bruker AXS, Madison,
Wisconsin, USA, 1998.
4.3. X-ray crystal data for 2a and 2c
Single crystals of the complexes 2a and 2c were obtained by
slow diffusion of pentane into the solutions of the complexes in
CH2Cl2 or benzene in NMR-tubes at room temperature.
The crystal X-ray diffraction experiments for compound 2a and
2c were carried out with a Bruker SMART
APEX II diffractometer
(graphite monochromated Mo K radiation, k = 0.71073 A, x-scan
a
technique, T = 100 K). The APEX II software [25] was used for col-
lecting frames of data, indexing reflections, determination of lattice
constants, integration of intensities of reflections, scaling and