Aminophosphines derived from 1-amino-4-methylpiperazine: Synthesis, oxidation and complexation reactions

Article abstract of DOI:10.1080/10426507.2011.650805

Functionalized mono(amino)phosphines of the type Ph₂PNHR (1) and bis (amino)phosphine of the type PhP(NHR)² (2) have been synthesized by treating Ph₂PCl or PhPCl₂ with 1-amino-4- methylpiperazine. Ligands react

Full text of DOI:10.1080/10426507.2011.650805

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Phosphorus, Sulfur, and Silicon and the
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Aminophosphines Derived From 1-
Amino-4-Methylpiperazine: Synthesis,
Oxidation and Complexation Reactions
Özlem Sarıöz a & Sena Öznergiz a
a Department of Chemistry, Faculty of Science-Arts, Niğde
University, Niğde, Turkey
Available online: 04 Jan 2012
To cite this article: Özlem Sarıöz & Sena Öznergiz (2012): Aminophosphines Derived From 1-Amino-4-
Methylpiperazine: Synthesis, Oxidation and Complexation Reactions, Phosphorus, Sulfur, and Silicon
and the Related Elements, 187:8, 906-913
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Phosphorus, Sulfur, and Silicon, 187:906–913, 2012
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2011.650805
AMINOPHOSPHINES DERIVED FROM
1-AMINO-4-METHYLPIPERAZINE: SYNTHESIS,
OXIDATION AND COMPLEXATION REACTIONS
¨
¨
Ozlem Sarıo¨z and Sena Oznergiz
Department of Chemistry, Faculty of Science-Arts, Nig˘de University, Nig˘de, Turkey
GRAPHICAL ABSTRACT
Abstract Functionalized mono(amino)phosphines of the type Ph2PNHR (1) and bis
(amino)phosphine of the type PhP(NHR)2 (2) have been synthesized by treating Ph2PCl or
PhPCl2 with 1-amino-4-methylpiperazine. Ligands react with aqueous hydrogen peroxide,
elemental sulfur, or selenium to give the corresponding chalcogenides in good yields. The
molybdenum complexes of the aminophosphines have been obtained. All of the new compounds
were characterized by IR, 1H, and 31P-NMR spectroscopy and elemental analysis.
Keywords Mono(amino)phosphine; bis(amino)phosphine; aminophosphine chalcogenides
INTRODUCTION
Phosphine ligands have many important applications in organometallic chemistry
and catalysis.1,2 If the phosphorus(III) center is chemically bonded to an amino substituent
(primary or secondary), an “aminophosphine” results. Therefore, an aminophosphine has
a tricoordinate P(III) center bound to a tricoordinate N(III) center. Aminophosphines have
proved their merits in various aspects of chemistry like sterochemistry, theoretical and
computational chemistry, organometallic and coordination chemistry, and catalysis and
inorganic heterocyclic chemistry.3 Functionalized aminophosphines with additional donor
groups attached onto the amine or phosphine backbones are particularly interesting since
the functional group can be modified to tune the chemical and physical properties of the
final product.4 The substituents enhance the importance of these compounds as they offer
Received 27 October 2011; accepted 14 December 2011.
Support of this work by TUBITAK (Project number 110T572) is gratefully acknowledged.
¨
Address correspondence to O. Sarıo¨z, Department of Chemistry, Faculty of Science-Arts, Nig˘de University,
Nig˘de, Turkey. E-mail: ozsarioz4@yahoo.com
906

AMINOPHOSPHINES
907
the possibility of manipulating them both on phosphorus and nitrogen besides, in principle,
granting nitrogen centers as additional donor sites toward metal substrates.3
Aminophosphine ligands have played a vital role in catalysis and organic conver-
sions and they have shown promising application potential in some electronic devices.3,5–9
Some aminophosphines and derivatives have also found application as anticancer drugs,
herbicides, and antimicrobial agents, as well as neuroactive agents.6 The P(V) derivatives
of aminophosphines have also proven useful as fire retardant agents, as chemotherapeutic
agents, as sterilizing agents, and as effective insecticides.3
Herein, we describe the synthesis of new aminophosphine ligands, their molybdenum
complexes and the corresponding aminophosphine chalcogenides of the general formula
Ph2P(E)NHR or PhP(E)(NHR)2. The compounds were fully characterized by IR, 1H NMR,
31P NMR spectroscopic techniques, and by elemental analysis.
RESULTS AND DISCUSSION
Synthesis of Ligands 1 and 2
Although many synthetic methods like condensation, scrambling, and transamination
reactions are reported in the literature, the condensation route is the most widely used and
the best one for synthesizing a wide variety of P(III)–N compounds.3
The reactions of 1-amino-4-methylpiperazine with diphenylchlorophosphine
or phenyldichlorophosphine afford the corresponding derivatives of aminophospines
Ph2PNHNC4H8NCH3 (1) and PhP(NHNC4H8NCH3)2 (2) in good yield. Oxidation of 1
and 2 by aqueous hydrogen peroxide or elemental sulfur or selenium gave the correspond-
ing oxides (3 and 6), sulfides (4 and 7), and selenides (5 and 8), respectively. The synthesis
of aminophosphine ligands (1–2) and their oxidation reactions are shown in Scheme 1.
Among the routes used to prepare aminophosphines, the most frequently used method
involves aminolysis of a chlorophosphine. The reaction of chlorophosphine and the primary
amine usually provides the target compound, RNHPR’2, in high yield. The reactions of
some primary amine derivatives with Ph2PCl in the presence of triethylamine have been
Scheme 1 Synthesis of aminophosphine ligands (1 and 2) and their oxidation reactions.

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O. SARIOZ AND S. OZNERGIZ
Table 1 Selected spectroscopic data for synthesized compounds
υ (cm–1
)
Compound
δ P (ppm) ꢀδ (ppm)
P
N
P
Ph
N
H
P
O
P
S
P Se
PPh2NHNC4H8NCH3
PPh(NHNC4H8NCH3)2
Ph2P(O)NHNC4H8NCH3
Ph2P(S)NHNC4H8NCH3
Ph2P(Se)NHNC4H8NCH3
PhP(O)(NHNC4H8NCH3)2
PhP(S)(NHNC4H8NCH3)2
PhP(Se)(NHNC4H8NCH3)2
[Mo(CO)4(Ph2PNHNC4H8NCH3)2]
[Mo(CO)4(PhP(NHNC4H8NCH3)2)2]
33.3
67.6
19.5
57.8
54.3
14.6
60.7
57.8
919
1432 3136
1436 3154
1437 3223 1158
1436 3196
1435 3139
1435 3227 1153
1436 3174
1436 3234
1434 3286
1437 3178
930
933
910
902
929
923
924
919
979
645
503
645
554
82.9
103.6
49.6
36.0
thoroughly studied and different substances were obtained, depending on the relative ratio
of the reagents, the electron-withdrawing groups and their positions on the aromatic ring
and solvents such as diethyl ether and dichloromethane. Aminophosphines (Ph2PNHR)
are found as the main products, and when the reaction conditions changed diphosphi-
noamines (RN(PPh2)2) or iminodiphosphines (R N PPh2-PPh2) are also formed as the
major products.10 The substituents at the amine backbone can also play an important role
in determining the outcome of the products.4
The structure of the compounds (1,2) was confirmed by spectroscopic analysis. The
1
spectroscopic data for synthesized compounds is shown in Table 1. The 31P-{ H} NMR
spectra of the aminophosphines show singlets at 33.3 ppm for 1 and 67.6 ppm for 2. The
absence of a signal at 81.5 or 160.2 ppm indicates that no unreacted PPh2Cl or PPhCl2
remained.11
We investigated the aminolysis reaction of 1-amino-4-methylpiperazine with Ph2PCl
in the presence of Et3N in tetrahydrofuran as solvent. In general, aminodiphenylphosphines
RNHPPh2 give rise to singlet resonances between 25 and 35 ppm. Diphosphinoamines (R-
N(PPh2)2) also exhibit a singlet resonance, but at higher frequency, typically around 64–70
ppm.10 There was no evidence for the formation of iminodiphosphine, producing two sets
1
of doublets at ≈+10 to ≈−20 ppm.12 The 31P-{ H} NMR spectrum of the product 1 shows
that the compound displays the characteristic signal of aminophosphine, and the result is
in agreement with the earlier studies.10
1
1
The H NMR spectra are consistent with the proposed structure. In the H NMR
spectra, the N H signals were observed as doublets at 4.28 ppm for 1 and 4.23 ppm for 2.13
In the IR spectra of the ligands, the υ(P N) vibration is tentatively assigned to a very
strong absorption at 919 cm−1 for 1 and 930 cm−1 for 2.13,14 Ligands 1 and 2 have υ(P Ph)
bands at 1432 and 1436 cm−1 and υ(N H) bands at 3136 and 3154 cm−1, respectively.15
Oxidation Reactions of 1 and 2
Oxidation of 1 and 2 by aqueous hydrogen peroxide or elemental sulfur or sele-
nium gave the corresponding oxides (3 and 6), sulfides (4 and 7) and selenides (5 and
8), respectively. Oxidation of 1–2 using aqueous H2O2 was very rapid even at ambient
temperature. However, the reaction with elemental sulfur or selenium had to be carried out

AMINOPHOSPHINES
909
at elevated temperatures, as expected because elemental sulfur and selenium are weaker
oxidizing agents than hydrogen peroxide, especially toward phosphorus atoms with bulky
phenyl groups.4 As is typical of P(V) E compounds, 31P chemical shifts of compounds
3–8 occurred in the δ 14.6–60.7 ppm range, and the chemical shift region is quite consistent
with the literature for analogous derivatives.4,16–19 As indicated in the literature, coupling
constants of 1JPSe 754.0 and 977.8 Hz are often seen for E Se.19
1
There is a well-established correlation between JPSe and the electronic properties
of the parent phosphorus ligands, which takes the form of an inverse relationship with
1
the σ–basicity. Thus, as expected, the values of the JPSe coupling constant decrease
in the order 8 > 5 which is consistent with the anticipated decrease in σ-basicity of
ligand as the number of piperazine substituents at the phosphorus atom increases. Thus,
Ph2P(Se)NHNC4H8NCH3 (8) is a better σ-donor than PhP(Se)(NHNC4H8NCH3)2 (5).19
The 1H NMR spectra of chalcogenides (3–8) are consistent with the proposed struc-
tures. In the 1H NMR spectra, the N H signals were observed in region of 3.20–4.15 ppm
as doublets.13,20 In the IR spectra of 3–8, the υ(P N) vibration is observed at 933 cm−1 (3),
910 cm−1 (4), 902 cm−1 (5), 929 cm−1 (6), 923cm−1 (7), and 924 cm−1 (8).15 The υ(P-Ph)
bands are observed in region of 1435–1437 cm−1. The υ(N-H) bands are observed in region
of 3139-3234 cm−1. The oxides 3 and 6 show υ(P O) vibration at 1158 for 3 and 1153
cm−1 for 6 respectively.17 The υ(P S) vibration is observed at 645 cm−1 for 4 and 7, and
υ(P Se) vibration at 503 for 5 and 554 cm−1 for 8 respectively.3 In the IR spectra of the
compounds, while the υ(P O) vibrations are observed in very narrow range, the υ(P N)
vibrations are observed in relatively wide range, suggesting that P(III) N bonds are quite
sensitive to the substituents attached to them.
The structures of the oxidized derivatives (3 and 4), sulfides (5 and 6) and selenides (7
and 8) were further confirmed by using microanalysis, and found to be in good agreement
with the theoretical values.
Complexation Reactions of 1 and 2
Themolybdenumcarbonylderivatives, cis-[Mo(CO)4(L)2][L=Ph2PNHNC4H8NCH3,
9; L = PhP(NHNC4H8NCH3)2, 10] were obtained by the displacement of bipyridine from
the [Mo(CO)4(bipy)].
The molybdenum carbonyl derivatives, cis-[Mo(CO)4(L)2] (9–10) were characterized
by IR, NMR, and elemental analysis. Ligands bearing both amine and tertiary phosphine
donors can behave as monodentate ligand (via P or N) or bidentate ligand (via P and
N). The P N bond in aminophosphines is essentially a single bond, so the lone pairs on
nitrogen and phosphorus are available for donor bonding toward metal atoms. However,
no examples have been synthesized where both P and N have acted as donor atoms. It is
only P which acts as the donor atom. The phosphorus chemical shift for the complexes
indicates P Mo interaction due to the low coordination shift value of complexes (ꢀδ). In
1
the 31P-{ H} NMR spectra, 9 and 10 exhibit singlets which show the expected low-field
shifts relative to the uncoordinated ligands [9: 82.9 ppm (ꢀδ = 49.6 ppm) and 10: 103.6
1
ppm (ꢀδ = 36.0 ppm)].13 The 31P–{ H} NMR chemical shifts of 9 and 10 are also within
the expected range for structurally similar complexes.
In the IR spectra of the metal carbonyl complexes, the υ(N-H) vibration is tentatively
assigned to a very strong absorption at 3286 cm−1 for 9 and 3178 cm−1 for 10 respectively,
which is shifted to higher wavenumbers compared with their free ligands.13 The υ(P N)
band is observed at 919 cm−1 for 9 and 979 cm−1 for 10 respectively.13,14 The υ(P Ph)

¨ ¨ ¨
O. SARIOZ AND S. OZNERGIZ
910
bands are observed at 1434 cm−1 for 9 and 1437 cm−1 for 10 respectively. The infrared
spectra of the complexes [Mo(CO)4L2] exhibit four intense υ(CO) absorptions, in the
carbonyl region (1776–2012 cm−1), characteristic of the presence of cis-[Mo(CO)4] with
C2v symmetry.4,21–24
The generation of [Mo(CO)4L2] complexes may be used to as a rapid “spot test” for
the donor properties of the incorporated ligands. This attribute has been recognized for many
years, and an extensive literature exists for these complexes, allowing ready comparison
with a variety of other phosphorus (III) ligands.1,25 The value υ(CO) has been used to
evaluate the ligand electronic properties.1 It was found that in the molybdenum complex
9, the CO stretching frequency (2009 cm−1) is lower than in the molybdenum complex 10
(2012 cm−1). Hence, the ligand Ph2PNHNC4H8NCH3 is slightly stronger σ-donor and a
little more electron rich than the ligand PhP(NHNC4H8NCH3)2.
EXPERIMENTAL
Reactions were routinely carried out using Schlenk-line techniques under pure dry
nitrogen gas. Solvents were dried and distilled prior to use. [Mo(CO)4(bipy)] was prepared
according to the literature.26 All other chemicals were reagent grade, available commercially
and used without further purification. Melting points were determined on a Electrothermal A
1
9100 and are uncorrected. 31P-{ H} and 1H NMR spectra were taken on Bruker UltraShield-
400 spectrophotometer. Infrared spectra were recorded on a Perkin Elmer FT-IR System
Spectrum BX. Elemental analyses were performed in a TruSpec Micro.
Preparation of PPh2NHNC4H8NCH3 (1)
Triethylamine (3.8 mL, 27.41 mmol) and Ph2PCl (5.0 mL, 27.19 mmol) were
sequentially added with stirring to a solution of 1-amino-4-methylpiperazine (3.3 mL,
27.22 mmol) in thf (20 mL). The reaction mixture was stirred for 5 h and then filtered to
remove Et3N.HCl. The resulting solution was evaporated under reduced pressure and the
product dissolved with diethyl ether in an acetone–dry ice bath. The mixture was allowed
to warm slowly to room temperature. The solvent was removed under vacuum to give a
white solid of the crude product, which was crystallized from CH2Cl2/diethyl ether mixture
(2:1) at 0 oC. Yield 6.92 g (85%). m.p.: 142–143 ◦C. 1H NMR (CDCl3, δ, ppm): 7.81 (dq,
Ph, J = 8 Hz, 4H), 7.50 (dq, Ph, J = 8 Hz, 6H), 4.28 (d, NH, J = 20 Hz, 1H), 2.87 (b,
HNN CH2, 4H), 2.53 (b, CH3N CH2, 4H), 2.29 (s, N CH3, 3H). 31P NMR (CDCl3, δ,
ppm): 33.3 (s). Selected IR (KBr pellet, cm−1): 919 (PN), 1432 (PPh), 3136 (NH). Elem.
Anal.: C17H22PN3 (299.35 gmol−1) Found (Required): C, 67.99 (68.21); H, 7.00 (7.41); N,
14.09 (14.04).
Preparation of PPh(NHNC4H8NCH3)2 (2)
A similar procedure to that described for 1 was used. Yield 4.34 g (70%). m.p.:
120–121 ◦C. 1H NMR (CDCl3, δ, ppm): 7.89 (dq, Ph, J = 8 Hz, 2H), 7.32 (dq, Ph, J = 8
Hz, 3H), 4.23 (d, NH, J = 16 Hz, 2H), 2.85 (b, HNN CH2, 8H), 2.51 (b, CH3N CH2,
1
8H), 2.28 (s, N CH3, 6H). 31P { H} NMR (CDCl3, δ, ppm): 67.6 (s). Selected IR (KBr
pellet, cm−1): 930 (PN), 1436 (PPh), 3154 (NH). Elem. Anal.: C16H29PN6 (336.42 gmol−1
Found (Required): C, 56.85 (57.12); H, 8.45 (8.69); N, 24.84 (24.98).
)

AMINOPHOSPHINES
911
Preparation of Ph2P(O)NHNC4H8NCH3 (3)
A thf solution (10 mL) of 1 (0.75 g, 2.51 mmol) and aqueous H2O2 (30% w/w, 0.3
mL) was stirred for 5 h at room temperature. The reaction mixture was concentrated to
ca. 1–2 mL in vacuo and diethylether (20 mL) was added. The precipitate was filtered and
dried in air to yield 3. Yield 0.43 g (54%). m.p.: 191–193 ◦C. 1H NMR (CDCl3, δ, ppm):
7.88 (dq, Ph, J = 8 Hz, 4H), 7.45 (dq, Ph, J = 8 Hz, 6H), 4.15 (d, NH, J = 16 Hz, 1H),
1
3.01 (b, HNN CH2, 4H), 2.56 (b, CH3N CH2, 4H), 2.32 (s, N CH3, 3H). 31P { H}
NMR (CDCl3, δ, ppm): 19.5 (s). Selected IR (KBr pellet, cm−1): 933 (PN), 1437 (PPh),
1158 (P O), 3223 (NH). Elem. Anal.: C17H22PN3O (315.35 gmol−1) Found (Required):
C, 64.76 (64.75); H, 7.00 (7.03); N, 13.09 (13.32).
Preparation of Ph2P(S)NHNC4H8NCH3 (4)
Ligand 1 (0.855 g, 2.86 mmol) and S8 (0.092 g, 2.87 mmol) were refluxed in toluene
(20 mL) for 9 h. The reaction mixture was concentrated to ca. 1–2 mL in vacuo and
diethylether (20 mL) was added. The precipitate was filtered and dried in air to yield 4.
Yield 0.62 g (65%). m.p.: 125–126 ◦C. 1H NMR (CDCl3, δ, ppm): 8.04 (dq, Ph, J = 8 Hz,
4H), 7.45 (dq, Ph, J = 8 Hz, 6H), 3.66 (d, NH, J = 20 Hz, 1H), 2.85 (b, HNN CH2, 4H),
1
2.42 (b, CH3N CH2, 4H), 2.24 (s, N CH3, 3H). 31P { H} NMR (CDCl3, δ, ppm): 57.8
(s). Selected IR (KBr pellet, cm−1): 910 (PN), 645 (PS), 1436 (PPh), 3196 (NH). Elem.
Anal.: C17H22PN3S (331.42 gmol−1) Found (Required): C, 61.45 (61.61); H, 6.82 (6.69);
N, 12.53 (12.68); S, 9.56 (9.67).
Preparation of Ph2P(Se)NHNC4H8NCH3 (5)
Ligand 1 (0.373 g, 1.25 mmol) and grey Se (0.1 g, 1.27 mmol) were refluxed in
toluene (20 mL) for 8 h. The reaction mixture was concentrated to ca. 1–2 mL in vacuo and
diethylether (20 mL) was added. The precipitate was filtered and dried in air to yield 5. Yield
0.32 g (68%). m.p.: 114–115 ◦C. 1H NMR (CDCl3, δ, ppm): 8.01 (dq, Ph, J = 8 Hz, 4H),
7.47 (dq, Ph, J = 8 Hz, 6H), 3.73 (d, NH, J = 20 Hz, 1H), 2.83 (b, HNN CH2, 4H), 2.45
1
(b, CH3N CH2, 4H), 2.27 (s, N CH3, 3H). 31P { H} NMR (CDCl3, δ, ppm): 54.3 (s,
JPSe = 754.0 Hz). Selected IR (KBr pellet, cm−1): 902 (PN), 503 (PSe), 1435 (PPh), 3139
(NH). Elem. Anal.: C17H22PN3Se (378.31 gmol−1) Found (Required): C, 53.68 (53.97); H,
5.58 (5.86); N, 11.29 (11.11).
Preparation of PhP(O)(NHNC4H8NCH3)2 (6)
A similar procedure to that described for 3 was used. Yield 0.55 g (70%). m.p.:
◦
1
173-174 C. H NMR (CDCl3, δ, ppm): 7.79 (dq, Ph, J = 8 Hz, 2H), 7.42 (dq, Ph, J =
8 Hz, 3H), 3.20 (d, NH, J = 16 Hz, 2H), 3.02 (t, HNN CH2, J = 4 Hz, 8H), 2.56 (t,
1
CH3N CH2, J = 4 Hz, 8H), 2.20 (s, N CH3, 6H). 31P { H} NMR (CDCl3, δ, ppm):
14.6 (s). Selected IR (KBr pellet, cm−1): 929 (PN), 1435 (PPh), 1153 (P O), 3227 (NH).
Elem. Anal.: C16H29PN6O (352.41 gmol−1) Found (Required): C, 54.39 (54.53); H, 8.14
(8.29); N, 23.56 (23.85).

¨
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912
O. SARIOZ AND S. OZNERGIZ
Preparation of PhP(S)(NHNC4H8NCH3)2 (7)
A similar procedure to that described for 4 was used. Yield 0.47 g (47%). m.p.: 83–84
◦C. 1H NMR (CDCl3, δ, ppm): 8.17 (dq, Ph, J = 8 Hz, 2H), 7.49 (dq, Ph, J = 8 Hz, 3H),
3.65 (d, NH, J = 20 Hz, 2H), 2.72 (b, HNN CH2, 8H), 2.53 (b, CH3N CH2, 8H), 2.28 (s,
1
N CH3, 6H). 31P { H} NMR (CDCl3, δ, ppm): 60.7 (s). Selected IR (KBr pellet, cm−1):
923 (PN), 645 (PS), 1436 (PPh), 3174 (NH). Elem. Anal.: C16H29PN6S (368.48 gmol−1
Found (Required): C, 51.85 (52.15); H, 7.82 (7.93); N, 22.53 (22.81); S, 8.53 (8.70).
)
Preparation of PhP(Se)(NHNC4H8NCH3)2 (8)
A similar procedure to that described for 5 was used. Yield 0.85 g (69%). m.p.:
◦
1
76–77 C. H NMR (CDCl3, δ, ppm): 8.19 (dq, Ph, J = 8 Hz, 2H), 7.50 (dq, Ph, J = 8
Hz, 3H), 3.79 (d, NH, J = 20 Hz, 2H), 2.71 (b, HNN CH2, 8H), 2.49 (b, CH3N CH2,
1
8H), 2.30 (s, N CH3, 6H). 31P { H} NMR (CDCl3, δ, ppm): 57.8 (s, JPSe = 977.8 Hz).
Selected IR (KBr pellet, cm−1): 924 (PN), 554 (PSe), 1436 (PPh), 3234 (NH). Elem. Anal.:
C16H29PN6Se (415.38 gmol−1) Found (Required): C, 46.18 (46.26); H, 6.89 (7.04); N,
19.96 (20.23).
Preparation of cis-[Mo(CO)4(Ph2PNHNC4H8NCH3)2] (9)
Ligand 1 (1.25 g, 4.18 mmol) and [Mo(CO)4(bipy)] (0.76 g, 2.09 mmol) were refluxed
in 20 mL CH2Cl2 for 5 h. The solution was concentrated in vacuo, and the purple product
was precipitated with diethylether (30 mL). The purple solid was separated by filtration and
washed with toluene (3 × 5 mL). Yield: 0.85 g (50%). m.p.: 200 ◦C (decomp). 1H NMR
(CDCl3, δ, ppm): 8.02 (dq, Ph, J = 8 Hz, 8H), 7.37 (dq, Ph, J = 8 Hz, 12H), 3.53 (d, NH, J =
24 Hz, 2H), 2.49 (b, HNN CH2, 8H), 2.43 (b, CH3N CH2, 8H), 2.37 (s, N CH3, 6H).
1
31P-{ H} NMR (CDCl3, δ, ppm): 82.9 (s). Selected IR (KBr pellet, cm−1): 919 (PN), 1434
(PPh), 2009, 1897, 1810, 1776 (CO), 3286 (NH). Elem. Anal.: C38H44P2N6O4Mo (806.68
gmol−1) Found (Required): C, 56.41 (56.58); H, 5.58 (5.50); N, 10.36 (10.42).
Preparation of cis-[Mo(CO)4(PhP(NHNC4H8NCH3)2)2] (10)
A similar procedure to that described for 9 was used. Yield: 0.49 g (70%). m.p.: 196
◦C (decomp). 1H NMR (CDCl3, δ, ppm): 7.86 (dq, Ph, J = 8 Hz, 4H), 7.45 (dq, Ph, J =
8 Hz, 6H), 3.05 (d, NH, J = 20 Hz, 4H), 2.95 (t, HNN CH2, J = 4 Hz, 16H), 2.45 (t,
1
CH3N CH2, J = 4 Hz, 16H), 2.22 (s, N CH3, 12H). 31P { H} NMR (CDCl3, δ, ppm):
103.6 (s). Selected IR (KBr pellet, cm−1): 979 (PN), 1437 (PPh), 2012, 1890, 1868, 1824
(CO), 3178 (NH). Elem. Anal.: C36H58P2N12O4Mo (880.81 gmol−1) Found (Required): C,
48.89 (49.09); H, 6.53 (6.64); N, 18.89 (19.08).
REFERENCES
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D. J. Chem. Soc., Dalton Trans. 2001, 7, 969-971.
2. Zubiri, M. R.; Milton, H. L.; Cole-Hamilton, D. J.; Slawin, A. M. Z.; Woollins, J. D. Inorg.
Chem. Commun. 2004, 7, 201-203.
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