Synthesis and structural studies of dimeric sodium compounds having pentametallacyclooctane and hexametallacyclo undecane structure using different phosphinamine derivatives

Article abstract of DOI:10.1016/j.molstruc.2012.09.077

The treatment of two bulky phosphinamines [Ph₂PNH(CHPh ₂)] (1) and [Ph₂PNH(CPh₃)] (2) with 30% hydrogen peroxide afforded phosphinicamides [Ph₂P(O)NH(CHPh ₂)] (3) and [Ph₂P(O)NHC

Full text of DOI:10.1016/j.molstruc.2012.09.077

Journal of Molecular Structure 1036 (2013) 188–195
Contents lists available at SciVerse ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Synthesis and structural studies of dimeric sodium compounds
having pentametallacyclooctane and hexametallacyclo undecane structure
using different phosphinamine derivatives
⇑
Ravi K. Kottalanka, Kishor Naktode, Tarun K. Panda
Department of Chemistry, Indian Institute of Technology Hyderabad, Ordnance Factory Estate, Yeddumailaram 502205, Andhra Pradesh, India
h i g h l i g h t s
"
"
"
"
Various bulky phosphinamines and derivatives have been synthesized.
Very straight forward synthesis, i.e. easily accessible of the compounds.
Novel structural motifs in sodium complexes using heteroatoms are observed.
Three hetero atoms (N, P, S or O) are making the poly metallacycles.
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 6 August 2012
Received in revised form 27 September 2012
Accepted 27 September 2012
Available online 9 October 2012
The treatment of two bulky phosphinamines [Ph2PNH(CHPh2)] (1) and [Ph2PNH(CPh3)] (2) with 30%
hydrogen peroxide afforded phosphinicamides [Ph2P(O)NH(CHPh2)] (3) and [Ph2P(O)NHCPh3] (4) in good
yield. When the same phosphinamines are reacted with elemental sulfur, corresponding sulfur
compounds [Ph2P(S)NH(CHPh2)] (5) and [Ph2P(S)NHCPh3] (6) are obtained. Further reactions of 4–6 with
sodium bis(trimethylsilyl)amide in THF solution afforded corresponding sodium salts of molecular
formula [{(THF)2Na(Ph2P(O)NCPh3)}2] (8), [{(THF)2Na(Ph2P(S)NCHPh2)}2] (7) and [{(THF)2Na(Ph2-
P(S)NCPh3)}{(THF)Na(Ph2P(S)NCPh3)}] (9) and all the sodium complexes 7–9 are dimeric and form highly
strained polymetallacyclic motif in solid state structures. Molecular structure of all the complexes are
established by single crystal X-ray diffraction analysis.
Keywords:
Phosphinamines
Polymetallacycles
Sodium
Ó 2012 Elsevier B.V. All rights reserved.
Sulfur
Phosphorus
1. Introduction
coordination sphere, may not only exhibit unusual co-ordination
modesbut also can be used for a number of catalytic transformations
Use of various PAN ligands is one of the alternatives of cyclopen-
tadienyl ligands and using this approach, amide ligands are success-
fully used today for the design of new transition-metal compounds
having well defined reaction centres [1,2]. Recently, there has been a
significant research effort in employing inorganic amines and imi-
nes. The PAN systems like monophosphanylamides (R2PNR0) [3–6]
diphosphanylamides ((Ph2P)2N) [4,7,8], phospho-raneiminato
(R3PN) [9], phosphiniminomethanides ½ððRNPR02Þ2CHÞꢀ [10–14],
phosphiniminomethandiides ððRNPR02Þ2CÞ [15–18], and dii-
minophosphinates (R2P(NR0) [19] are well known today as ligands
and proved their potency into the transition and f-block metals. Roe-
sky and co-workers introduced one chiral phosphinamine
HN(CHMePh)(PPh2) into the early transition-metal chemistry as
well as in lanthanide chemistry [20]. It was shown that some of
the early transition metal complexes having PAN ligands in the
such as polymerization reactions [21]. Very recently, Fryzuk and
co-workers have reported a series of three member lanthanide phos-
phinamido complexes by using alkane elimination route [22]. Other
approach to introduce the ligand system into the metal chemistry is
salt metathesis reaction. In our on-going project, we have synthe-
sized various transition metal complexes of N-(diphenylphos-
phino)-2,6-dimethylaniline [Ph2PNH(2,6-Me2C6H3)] and their
chalcogenides [Ph2P(O)NH(2,6-Me2C6H3)] and [Ph2P(S)NH(2,6-
Me2C6H3)] [23]. To get more insight about the influence of various
phosphinamine ligands toward the transition and lanthanide chem-
istry we decided to use the salt metathesis reaction involving metal
halides and alkali metal salts of the ligand. Therefore, we planned a
series of alkali metal salts of various phosphinamines and their
derivatives.
Herein we report the syntheses and structural studies of two
bulky phosphinamines [Ph2PNH(CHPh2)] (1) and [Ph2PNH(CPh3)]
(2) and their chalcogen derivatives [Ph2P(O)NH(CHPh2)] (3) and
⇑
Corresponding author. Tel.: +91 40 2301 6036; fax: +91 40 2301 6032.
E-mail address: tpanda@iith.ac.in (T.K. Panda).
0022-2860/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molstruc.2012.09.077

R.K. Kottalanka et al. / Journal of Molecular Structure 1036 (2013) 188–195
189
[Ph2P(O)-NH(CPh3)] (4), [Ph2P(S)NH(CHPh2)] (5) and [Ph2P(S)
2.4. Synthesis of Ph2P(O)NHCHPh2 (3)
NH(CPh3)] (6) along with various polycyclic structural motifs
formed by the sodium complexes [{(THF)2Na(Ph2P(O)NCPh3)}2]
(8), [{(THF)2Na(Ph2P(S)NCHPh2)}2] (7) and [{(THF)2Na(Ph2P(S)
NCPh3)}{(THF)Na(Ph2P(S)NCPh3)}] (9) with these compounds.
A 30% solution of H2O2 (0.15 ml) was added to a THF solution
(10 ml) of N-benzhydryl-1,1-diphenylphosphinamine (500 mg,
1.46 mmol) with stirring and cooling. When the exothermal pro-
cess finished the mixture was evaporated in vacuo. A white powder
was formed, which was washed with n-pentane and then dried in
vacuo. Yield was 0.525 g (100%). 1H NMR (400 MHz, CDCl3): d 7.73–
7.78 (m, 4H, ArH), 7.36–7.39 (m, 2H, ArH), 7.26–7.31 (m, 4H, ArH),
7.14–7.24 (m, 10H, ArH), 5.34–5.40 (t, 1H, J = 10.84 Hz, CH), 3.16–
3.19 (t, 1H, J = 9.09 Hz, NH) ppm. 13C{1H} NMR (100 MHz, CDCl3):
d 143.4 (ArC),143.3 (ArC), 132.9 (P-ArC), 132.3 (P attached o-ArC),
132.2 (P attached o-ArC), 131.9 (P attached p-ArC), 131.6 (P-ArC),
128.5 (m-ArC), 128.4 (P attached m-ArC), 128.3 (P attached m-
ArC), 127.6 (o-ArC), 127.2 (p-ArC), 58.6 (CH) ppm. 31P{1H}NMR
(161.9 MHz, CDCl3): d 23.4 ppm. FT-IR (selected frequencies):
2. Experimental
2.1. General
All manipulations of air-sensitive materials were performed
with the rigorous exclusion of oxygen and moisture in flame-dried
Schlenk-type glassware either on a dual manifold Schlenk line,
interfaced to a high vacuum (10ꢁ4 torr) line, or in an argon-filled
M. Braun glove box. THF was pre-dried over Na wire and distilled
under nitrogen from sodium and benzophenone ketyl prior to
use. Hydrocarbon solvents (toluene and n-pentane) were distilled
under nitrogen from LiAlH4 and stored in the glove box. 1H NMR
(400 MHz), 13C{1H} and 31P{1H} NMR (161.9 MHz) spectra were
recorded on a BRUKER AVANCE III-400 spectrometer. BRUKER
ALPHA FT-IR was used for FT-IR measurement. Elemental analyses
were performed on a BRUKER EURO EA at the Indian Institute of
Technology Hyderabad. The starting materials chlorodiphenyl-
phosphine, benzdihydrylamine, triphenylmethyl amine, sodium
bis(trimethyl)silylamide were purchased from Sigma Aldrich and
used without further purification. The NMR solvent C6D6 and
CDCL3 were purchased from sigma Aldrich.
m
= 3196 (NAH), 1435 (PAC), 997 (PAN), 1181 (P@O) cmꢁ1. Ele-
mental Analysis (C25H22NPO): Calcd. C 78.31, H 5.78, N 3.65; Found
C 77.79, H 5.61, N 3.42.
2.5. Synthesis of Ph2P(O)NHCPh3 (4): same as above for compound 3
Yield was 0.525 g (100%). 1H NMR (400 MHz, CDCl3): d 7.61–
7.66 (m, 4H, ArH), 7.15–7.28 (m, 13H, ArH), 7.08–7.09 (m, 8H,
ArH), 4.20–4.19 (d, 1H, J = 5.12 Hz, NH) ppm. 13C{1H} NMR
(100 MHz, CDCl3): d 144.0 (ArC),143.9 (ArC), 134.3 (P-ArC), 133.0
(P-ArC), 130.6 (P attached o-ArC), 130.5 (P attached o-ArC), 130.0
(P attached p-ArC), 128.5 (m-ArC), 127.2 (P attached m-ArC),
127.1 (P attached m-ArC), 126.6 (o-ArC), 126.2 (p-ArC), 70.2 (tri-
phenylmethyl C) ppm. 31P{1H}NMR (161.9 MHz, CDCl3):
d
18.4 ppm. FT-IR (selected frequencies):
m
= ꢂ3300 (very week
broad NAH), 1439 (PAC), 866 (PAN), 1184 (P@O) cmꢁ1. Elemental
Analysis (C31H26NPO): Calcd. C 81.03, H 5.70, N 3.05; Found C
80.75, H 5.31, N 2.87.
2.2. Synthesis of Ph2PNHCHPh2 (1)
In a flame dried Schlenk flask 1.32 g (6.0 mmol) of chlorodi-
phenylphosphine was dissolved in 5 ml of dry toluene. To this solu-
tion, 2.19 g (12.0 mmol) of benzhdrylamine in 5 ml of dry toluene
was added dropwise under stirring at 0 °C, immediate white tur-
bidity was observed. The solution mixture was stirred for another
3 h at room temperature, and then white precipitate was filtered
by using G4 frit and filtrate is collected. Solvent was removed in va-
cuo; pale yellow colored powder is obtained. Yield was 2.0 g (90%).
1H NMR (400 MHz, CDCl3): d 7.00–7.34 (m, 20H, ArH), 5.26–5.37
(dd, 1H, J = 6.67 Hz, 2.37 Hz, CH), 2.52 (br t, 1H, J = 6.5 Hz, NH)
ppm. 13C{1H} NMR (100 MHz, CDCl3): d 144.8 (ArC), 144.7(ArC),
141.9 (P-ArC), 141.8 (P-ArC), 131.4 (P attached o-ArC), 131.2 (P at-
tached o-ArC), 128.5 (m-ArC), 128.4 (o-ArC), 128.2 (P attached p-
ArC), 128.1 (P attached p-ArC) 127.4 (P attached m-ArC), 126.9
(p-ArC), 65.2, 65.0 (CH) ppm. 31P{1H}NMR (161.9 MHz, CDCl3): d
2.6. Synthesis of Ph2P(S)NHCHPh2 (5)
N-benzhydryl-1,1-diphenylphosphinamine (300 mg, 0.82 mmol)
and elemental sulfur S8 (26.3 mg, 0.82 mmol) were heated to
60 °C in toluene (5 ml) for 6 h. After removal of solvent in vacuo
white solid was obtained. (Yield: 300 mg, (92%). The title com-
pound Ph2P(S)NHCHPh2 recrystallized from hot toluene. 1H NMR
(400 MHz, CDCl3): d 7.74–7.79 (m, 4H, ArH), 7.32–7.36 (m, 2H,
ArH), 7.12–7.28 (m, 12H, ArH), 5.58–5.64 (dd, 1H, J = 8.71 Hz,
5.72 Hz, CH), 3.16–3.19 (dd, 1H, J = 5.21 Hz, J = 2.58 Hz, NH) ppm.
13C{1H} NMR (100 MHz, CDCl3): d 143.2 (ArC),143.1 (ArC), 134.7
(P-ArC), 133.7 (P-ArC), 131.8 (P attached o-ArC), 131.7 (P attached
o-ArC), 131.6 (P attached p-ArC), 131.5 (P attached p-ArC), 128.4
(m-ArC), 128.3 (P attached m-ArC), 128.2 (P attached m-ArC),
127.8 (o-ArC), 127.2 (p-ArC), 58.9 (CH) ppm. 31P{1H}NMR
(161.9 MHz, CDCl3): d 60.3 ppm. FT-IR (selected frequencies):
35.2 ppm. FT-IR (selected frequencies):
m = 3262 (NAH), 1432
(PAC), 876 (PAN) cmꢁ1. Elemental Analysis (C25H22NP): Calcd. C
81.72, H 6.04, N 3.81; Found C 80.96, H 5.82, N 3.43.
m
= 3261 (NAH), 1432 (PAC), 902 (PAN), 625 (P@S) cmꢁ1. Elemen-
tal Analysis (C25H22NPS): Calcd. C 75.16, H 5.55, N 3.51; Found C
2.3. Synthesis of Ph2PNHCPh3 (2): same as above for 1
74.87, H 5.44, N 3.37.
Yield is 2.0 g (90%). 1H NMR (400 MHz, CDCl3): d 7.29–7.31 (m,
6H, ArH), 7.06–7.16 (m, 19H, ArH), 3.06 (d, 1H, J = 9.8 Hz, NH) ppm.
13C{1H} NMR (100 MHz, CDCl3): d 147.4 (ArC),147.3 (ArC), 135.3
(P-ArC), 135.2 (P-ArC), 131.3 (P attached o-ArC), 131.2 (P attached
o-ArC), 128.9 (o-ArC), 128.2 (P attached p-ArC), 128.1 (P attached
m-ArC), 128.0 (P attached m-ArC), 127.8 (m-ArC), 126.5 (p-ArC),
71.32 (triphenylmethyl C) ppm. 31P{1H}NMR (161.9 MHz, CDCl3):
2.7. Synthesis of Ph2P(S)NHCPh3 (6): same as above for compound 5
Yield: 500 mg, (92%). The title compound [Ph2P(S)NHCPh3]
recrystallized from hot toluene. 1H NMR (400 MHz, CDCl3): d
7.20–7.31 (m, 13H, ArH), 7.08–7.17 (m, 12H, ArH), 3.92 (d, 1H,
J = 4.2 Hz, NH) ppm. 13C{1H} NMR (100 MHz, CDCl3): d 143.8
(ArC),143.7 (ArC), 135.8 (P-ArC), 134.8 (P-ArC), 130.4 (P attached
o-ArC), 130.3 (P attached o-ArC), 129.9 (P attached p-ArC), 129.8
(P attached p-ArC), 128.8 (m-ArC), 127.2 (P attached m-ArC),
127.1 (P attached m-ArC), 126.5 (o-ArC), 126.2 (p-ArC), 70.9
(triphenylmethyl C) ppm. 31P{1H}NMR (161.9 MHz, CDCl3): d
d 26.3 ppm. FT-IR (selected frequencies):
m
= ꢂ3300 (very week
broad NAH), 1434 (PAC), 896 (PAN) cmꢁ1. Elemental Analysis
(C31H26NP): Calcd. C 83.95, H 5.91, N 3.16; Found C 83.26, H
5.72, N 2.91.

190
R.K. Kottalanka et al. / Journal of Molecular Structure 1036 (2013) 188–195
53.3 ppm. FT-IR (selected frequencies):
m
= 3359 (NAH), 1437
nitrogen stream at 150(2) K. All measurements were made on an
Oxford Supernova X-calibur Eos CCD detector with graphite-
(PAC), 860 (PAN), 640 (P@S) cmꢁ1. Elemental Analysis (C31H26-
NPS): Calcd. C 78.29, H 5.51, N 2.95; Found C 77.86, H 5.32, N 2.71.
monochromatic CuKa (1.54184 Å) radiation. Crystal data and
structure refinement parameters are summarized in Table 1. The
structures were solved by direct methods (SIR92) [29] and refined
on F2 by full-matrix least-squares methods; using SHELXL-97 [30].
Non-hydrogen atoms were anisotropically refined. H-atoms were
included in the refinement on calculated positions riding on their
2.8. Synthesis of [{Na(THF)2Ph2P(S)NH(CHPh2)}2] (7)
In a 10 ml sample viol 1 equivalent (50 mg, 0.125 mmol) of ligand
5 and 1 equivalent of sodium bis(trimethyl)silylamide (23 mg,
0.125 mmol) were mixed together with small amount of toluene,
after 6 h small amount of THF and n-pentane were added to it and
kept in ꢁ40 °C freezer, after 24 h sodium-PNS complex crystals were
obtained. 1H NMR (400 MHz, C6D6): d 7.82–7.87 (m, 4H, ArH), 7.07
(m, 4H, ArH), 6.82–7.06 (m, 12H, ArH), 5.78–5.84 (dd, 1H,
J = 8.88 Hz, 5.88 Hz CH) ppm, 3.45–3.48 (m, THF), 1.29–1.33 (m,
THF) ppm. 13C{1H} NMR (100 MHz, C6D6): d 143.8 (ArC),143.7
(ArC), 135.9 (P-ArC), 134.9 (P-ArC), 132.2 (P attached o-ArC), 132.1
(P attached o-ArC), 131.2 (P attached p-ArC), 131.1 (P attached p-
ArC), 128.4 (P attached m-ArC), 128.2 (m-ArC), 127.9 (o-ArC),
127.1 (p-ArC), 58.9 (CH) ppm. 31P{1H} NMR (161.9 MHz, C6D6): d
carrier atoms. The function minimized was
(w = 1/[
[
R
w(Fo2 ꢁ Fc2)2]
r
2 (Fo2) + (aP)2 + bP]), where P = (Max(Fo2, 0) + 2Fc2)/3 with
r
2(Fo2) from counting statistics. The function R1 and wR2 were
(R
||Fo| ꢁ |Fc||)/
R
|Fo| and [
R
R
w(Fo2 ꢁ Fc2)2/ (wFo4)]1/2, respectively.
The ORTEP-3 program was used to draw the molecule. Crystallo-
graphic data (excluding structure factors) for the structures re-
ported in this paper have been deposited with the Cambridge
Crystallographic Data Centre as a supplementary publication no.
CCDC 889246-889251. Copies of the data can be obtained free of
charge on application to CCDC, 12 Union Road, Cambridge CB21EZ,
UK (fax: +44 1223 336 033; email: deposit@ccdc.cam.ac.uk).
73.3 ppm. Elemental Analysis (C66H74N2Na2O4P2S2): Calcd.
70.07, H 6.59, N 2.48; Found C 69.88, H 6.25, N 2.33.
C
3. Results and discussion
2.9. Synthesis of [{Na(THF)2Ph2P(O)NH(CPh3)}2] (8)
The phosphinamines [Ph2PNH(CHPh2)] (1) and [Ph2PNH(CPh3)]
(2) were prepared in good yield by the aminolysis reaction by the
respective amines, and diphenylphosphine chloride in 2:1 molar ra-
tion at room temperature by using toluene solvent (Scheme 1) [24].
In 31P {1H} NMR spectra compound 1 shows a signal at 35.2 ppm
In a 10 ml sample vial 1equivalent (50 mg, 0.105 mmol) of li-
gand 6 and 1 equivalent of sodium bis(trimethyl)silylamide (23
mg, 0.125 mmol) were mixed together with small amount of tolu-
ene, after 6 h small amount of THF and n-pentane were added to it
and kept in ꢁ40 °C freezer, after 24 h complex 9 crystals were ob-
tained. 1H NMR (400 MHz, C6D6): d 7.73–7.68 (m, 3H, ArH), 7.39–
7.38 (m, 4H, ArH), 7.06–6.82 (m, 18H, ArH) ppm. 13C{1H} NMR
(100 MHz, C6D6): d 143.8 (ArC), 143.7 (ArC), 135.8 (P-ArC), 134.8
(P-ArC), 130.4 (P attached o-ArC), 130.3 (P attached o-ArC), 129.9
(P attached p-ArC), 129.8 (P attached p-ArC), 128.8 (m-ArC),
127.2 (P attached m-ArC), 127.1 (P attached m-ArC), 126.5 (o-
ArC), 126.2 (p-ArC), 70.9 (triphenylmethyl C) ppm. [{(THF)2Na(Ph2-
P(S)NCHPh2)}2] (7) NMR (161.9 MHz, C6D6): d 73.1 ppm. Elemental
Analysis (C74H74N2Na2O3P2S2): Calcd. C 73.37, H 6.16, N 2.31;
Found C 73.05, H 5.96, N 1.99.
which is slightly downfield shifted to that of compound
2
(26.3 ppm). Compound 1 crytallizes in monoclinic space group Cc
whereas compound 2 crystallizes in monoclinic space group P21/c.
The structural parameters and selected bond distances, bond angles
are given Tables 1 and 2 respectively. In the solid state structure of
the compound 1 and 2 show similar PAN distances which are within
the range of reported values (Table 2) [25]. The respective phosphi-
nic amides [Ph2P(O)NH(CHPh2)] (3) and [Ph2P(O)NH(CPh3)] (4)
were prepared in high yield by the straightforward reactions involv-
ing compounds 1 or 2 with aqueous hydrogen peroxide in 1:1 molar
ratio at room temperature in THF (Scheme 1) [24]. In FT-IR spectra of
3 and 4, a strong absorption (1181 and 1184 cmꢁ1) is observed and
can be assigned as P@O bond stretching frequency along with the
absorbance for PAN (997 and 866 cmꢁ1), and NAH (3196 and
3300 cmꢁ1) bond stretching which are well in the expected ranges
[26]. In the 31P{1H} NMR spectra one signal is observed at 23.4 and
18.4 ppm for compound 3 and 4 respectively, representing slightly
high field shift compare to their respective phosphinamines.
The compounds 5 and 6 were prepared over 90% yield by the
reaction involving compound 1 or 2 and elemental sulfur in 1:1
molar ratio at room temperature in toluene (Scheme 2) [24]. In
FT-IR spectra of compounds 5 and 6, the strong absorptions at
625 and 640 cmꢁ1 respectively are observed which can be assigned
as P@S bond stretching frequency. In the 31P{1H} NMR spectra, one
signal (60.3 for 5, and 53.3 ppm for 6) is observed representing sig-
nificantly low field shift compare to their respective phosphin-
amine compounds. In the solid state, compound 6 crystallizes in
the monoclinic space group P21/c having four molecules in the unit
cell (Table 1). The phosphorus atom is tetra-coordinated by two
phenyl carbons, one nitrogen atom and one sulfur atom (Fig. 1).
The PAS distance 1.9472(8) Å (Table 2) are well agreement to con-
sider the PAS bond as double bond and compatible with literature
values (1.4921(7) Å) [25,26].
2.10. Synthesis of [{Na(THF)2Ph2P(S)N(CPh3)} {Na(THF)Ph2P(S)-
N(CPh3)}] (9)
In a 10 ml sample vial 1equivalent (50 mg, 0.105 mmol) of ligand
6 and 1 equivalent of sodium bis(trimethyl)silylamide (23 mg, 0.125
mmol) were mixed together with small amount of toluene, after 6 h
small amount of THF and n-pentane were added to it and kept in
ꢁ40 °C freezer, after 24 h complex 9 crystals were obtained. 1H
NMR (400 MHz, C6D6): d 7.73–7.68 (m, 3H, ArH), 7.39–7.38 (m, 4H,
ArH), 7.06–6.82 (m, 18H, ArH) ppm. 13C{1H} NMR (100 MHz, C6D6):
d 143.8 (ArC), 143.7 (ArC), 135.8 (P-ArC), 134.8 (P-ArC), 130.4 (P at-
tached o-ArC), 130.3 (P attached o-ArC), 129.9 (P attached p-ArC),
129.8 (P attached p-ArC), 128.8 (m-ArC), 127.2 (P attached m-ArC),
127.1 (P attached m-ArC), 126.5 (o-ArC), 126.2 (p-ArC), 70.9 (triphen-
ylmethyl C) ppm. [{(THF)2Na(Ph2P(S)NCHPh2)}2] (7) NMR
(161.9 MHz, C6D6): d 73.1 ppm. Elemental Analysis (C74H74N2Na2O3-
P2S2): Calcd. C 73.37, H 6.16, N 2.31; Found C 73.05, H 5.96, N 1.99.
2.11. X-ray crystallographic studies
Single crystals of compounds 1, 2 were grown from a solution of
CH2Cl2 at a temperature of ꢁ4 °C, compound 6 from hot toluene
under argon atmosphere whereas crystals of compounds 7–9 were
grown from toluene, THF and pentane mixture. In each case a crys-
tal of suitable dimensions was mounted on a CryoLoop (Hampton
Research Corp.) with a layer of light mineral oil and placed in a
3.1. Sodium salts
The dimeric sodium complex of molecular formula [{(THF)2Na
(Ph2P(S)NCHPh2)}2] (7) was prepared by the reaction of compound

R.K. Kottalanka et al. / Journal of Molecular Structure 1036 (2013) 188–195
191
Table 1
Crystal data and structure refinement for 1, 2 and 6–9.
CCDC No.
889249
25H22 N1 P1
367.41
150(2)
889247
889251
Empirical formula
Formula weight
T (K)
C
C31H26N1P1
443.5
150(2)
C31H26N1P1S1
475.56
150(2)
k (Å)
1.54184
Monoclinic,
Cc
22.237(4)
10.648(2)
9.551(2)
90
1.54184
Monoclinic
P21/c
8.9955(8)
18.6976(16)
15.5059(19)
90
1.54184
Monoclinic
P21/c
14.5362(5)
10.9798(4)
15.6321(4)
90
Crystal system
Space group
a (Å)
b (Å)
c (Å)
a
(°)
b (°)
112.38(3)
90
2091.1(7)
4
1.167
1.208
108.089(9)
90
2479.1(4)
4
1.188
1.106
90.970(3)
90
2494.60(14)
4
1.266
1.896
a
(°)
V (Å3)
Z
Dcalc g cmꢁ3
l
(mmꢁ1
)
F (000)
776
936
1000
Theta range for data collection
Limiting indices
Reflections collected/unique
4.30–71.25°.
3.82–70.76°
3.04–70.81°
–27 6 h 6 18, ꢁ11 6 k 6 12, ꢁ10 6 l 6 11
ꢁ10 6 h 6 9, ꢁ16 6 k 6 22, ꢁ15 6 l 6 18
ꢁ16 6 h 6 17, ꢁ13 6 k 6 11, ꢁ19 6 l 6 18
3859/2385
10,162/4624
10,314/4704
[R(int) = 0.0432]
97.10%
Empirical
[R(int) = 0.0776]
97.00%
Empirical
[R(int) = 0.0287]
97.80%
Empirical
Completeness to theta = 71.25
Absorption correction
Max. and min. transmission
Refinement method
0.880 and 0.790
Full-matrix
0.876 and 0.81
Full-matrix
0.738 and 0.616
Full-matrix
Least-squares on F2
2385/2/245
Least-squares on F2
4624/0/299
Least-squares on F2
4704/0/307
Data/restraints/parameters
Goodness-of-fit on F2
0.962
0.96
1.028
Final R indices [I > 2 sigma(I)]
R indices (all data)
Absolute structure parameter
Largest diff. peak and hole
R1 = 0.0774, wR2 = 0.1949
R1 = 0.0889, wR2 = 0.2104
0.12(7)
R1 = 0.0807, wR2 = 0.1766
R1 = 0.1970, wR2 = 0.2671
0.0029(4)
R1 = 0.0446, wR2 = 0.1143
R1 = 0.0541, wR2 = 0.1232
0.303 and ꢁ0.262 e Aꢁ3
0.326 and ꢁ0.365 e Aꢁ3
0.580 and ꢁ0.345 e Aꢁ3
7
8
9
CCDC No.
Empirical formula
Formula weight
T (K)
889246
66H74N2Na2O4P2S2
1131.33
150(2)
889248
C78 H82 N2 Na2 O6 P2
1251.38
889250
C74 H74 N2 Na2 O3 P2 S2
1211.42
C
150(2)
150(2)
k (Å)
1.54184
Triclinic
P ꢁ 1
1.54184
Triclinic
P ꢁ 1
1.54184
Triclinic
P ꢁ 1
Crystal system
Space group
a (Å)
b (Å)
c (Å)
10.5054(11)
12.9521(12)
13.3762(13)
108.731(9)
108.054(9)
104.940(9)
1504.2(3)
1
11.0777(13)
13.3008(18)
14.0442(19)
100.720(11)
112.259(12)
111.066(12)
1658.1(4)
1
10.7308(6)
11.6146(8)
26.1362(17)
79.662(6)
85.030(5)
78.126(5)
3131.8(3)
2
a
(°)
b (°)
a
(°)
V (Å3)
Z
Dcalc g cmꢁ3
1.249
1.83
1.253
1.163
1.285
1.784
l
(mmꢁ1
)
F (000)
600
664
1280
Theta range for data collection 3.86–70.69°
3.67–71.07°
3.44–71.04°
Limiting indices –
Reflections collected/unique
ꢁ12 6 h 6 12, ꢁ15 6 k 6 15, ꢁ16 6 l 6 16 ꢁ12 6 h 6 13, ꢁ15 6 k 6 16, ꢁ17 6 l 6 11 ꢁ12 6 h 6 11, ꢁ14 6 k 6 14, ꢁ31 6 l 6 22
10,292/5570
11,652/6230
20,573/11,831
[R(int) = 0.0346]
97.60%
[R(int) = 0.0514]
96.20%
[R(int) = 0.0643]
97.10%
Completeness to theta = 71.25
Absorption correction
Empirical
Empirical
Empirical
Max. and min. transmission
Refinement method
0.71 and 0.60
Full-matrix
0.890 and 0.810
Full-matrix
0.740 and 0.630
Full-matrix
Least-squares on F2
5570/0/352
Least-squares on F2
6230/0/406
Least-squares on F2
11,831/1/782
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2 sigma(I)]
R indices (all data)
1.036
1.054
1.027
R1a = 0.0582, wR2b = 0.1528
R1a = 0.0862, wR2b=0.1721
R1a = 0.0679, wR2b = 0.1603
R1a = 0.1215, wR2b=0.1965
R1a = 0.0600, wR2b = 0.1639
R1a = 0.0857, wR2b=0.1883
Absolute structure parameter
Largest diff. peak and hole
0.551 and ꢁ0.376 e Aꢁ3
0.274 and ꢁ0.434 e Aꢁ3
0.681 and ꢁ0.500 e Aꢁ3
a
R1(F) =
R
||Fo| ꢁ |Fc||/
R|Fo|.
b
wR2(F2) = [
R
w(Fo2 ꢁ Fc2)2/
R .
(wFo4)]1/2

192
R.K. Kottalanka et al. / Journal of Molecular Structure 1036 (2013) 188–195
Scheme 1. Syntheses of compounds 1–6.
Table 2
Selected bond lengths (Å) and angles (°) of 1, 2, 6, 7, 8 and 9.
1
2
6
7
8
9
Bond Length (Å)
P(1)AN(1)
1.673(6)
1.6907(17)
1.494(2)
1.6768(17)
1.9472(7)
1.485(2)
1.593(3)
1.9934(12)
1.471(4)
1.564(3)
1.520(2)
1.448(4)
1.583(2)
2.0133(10)
1.473(3)
P(1)AXa (1)
N(1)AC(1)
1.453(8)
1.842(6)
1.841(6)
P(1)AC(14)
P(1)AC(20)
P(1)AC(26)
Na(1)AN(1)
Na(1)AXa (1)
Na(1)AXa (2)
Na(1)AP(1)
Na(2)AXa (1)
Na(1)AC(19)
Na(1)AC(10)
1.828(2)
1.862(2)
1.816(2)
1.822(2)
2.381(3)
2.792(3)
2.369(3)
2.218(3)
3.0348(17)
2.430(2)
2.9521(15)
2.8570(16)
3.1733(14)
2.8570(16)
2.758(15)
2.8498(15)
3.1367(13)
3.1553(16)
3.086(4)
3.017(3)
Bond angle (°)
P(1)AN(1)AC(1)
118.2(4)
125.2(3)
129.55(13)
116.70(6)
112.56(7)
114.19(7)
113.26(14)
111.62(10)
111.54(11)
136.8(3)
134.87(18)
108.69(9)
104.17(10)
108.05(10)
103.36(13)
N(1)AP(1)AXa (1)
Xa (1)AP(1)AC(20)
Xa (1)AP(1)AC(26)
C(20)AP(1)AC(26)
C(14)AC(1)AN(1)
C(20)AP(1)AN(1)
C(26)AP(1)AN(1)
N(1)ANa(1)AP(1)
N(1)ANa(1)AXa (1)
N(1)ANa(1)AXa (2)
P(1)ANa(1)AXa (1)
P(1)ANa(1)AXa (2)
Xa (1)ANa(1)AXa (2)
Na(1)AP(1)AXa (1)
Na(1)AXa (1)ANa(2)
114.94(15)
105.14(15)
106.51(16)
105.20(17)
98.1(3)
99.5(2)
113.4(5)
103.0(3)
104.2(3)
108.9(4)
101.3(2)
101.5(2)
107.70(17)
116.37(16)
30.79(6)
59.85(9)
112.08(10)
29.52(6)
141.92(9)
82.70(10)
50.16(10)
97.30(10)
115.74(13)
115.97(13)
29.73(5)
68.52(6)
134.94(8)
39.29(2)
118.67(5)
96.02(4)
60.15(4)
84.96(4)
29.11(6)
66.87(7)
118.37(8)
37.77(3)
115.24(5)
99.43(4)
77.15(4)
80.57(4)
a
Here X = S for 6,7 and 9 and X = O for 8.
Scheme 2. Synthesis of compounds 7.
5 sodium bis(trimethyl)silylamide in toluene through the elimina-
tion of volatile bis(trimethyl)silylamine (Scheme 2) [24]. The com-
plex 7 crystallizes in triclinic space group P-1 having one molecule
in the unit cell (Table 1). Selected bond lengths and angles are gi-
ven in Table 2. In the centrosymmetric molecule 7, two phos-
phinthioic amide ligands are coordinating to two sodium atoms
by one sulfur, one phosphorus and one amido nitrogen atom exhib-
iting a diamond shaped Na2S2 core with mean S1ANaAS1i of

R.K. Kottalanka et al. / Journal of Molecular Structure 1036 (2013) 188–195
193
Fig. 1. Solid state structure of compound 1 (a) 2 (b) and 6 (c). Selected bond lengths [Å] and bond angles [°]: 1: P1AN1 1.673(6), N1AC1 1.453(8), P1AC20 1.841(6), P1AC14
1.842(6), C1AN1AP1 118.2(4), N1AP1 C20 103.0(3), N1AP1AC14 104.2(3), C20AP1AC14 98.1(3); 2; P1AN1 1.692(4), N1AC1 1.487(6), P1AC20 1.844(6), P1AC28 1.831(5),
C1AN1AP1 125.2(3), N1AP1AC20 101.3(2), N1AP1AC26 101.5(2), C26AP1AC20 99.5(2). 6: P1AN1 1.6768(17), P1AS1 1.9472(7), P1AC20 1.816(2), PAC26 1.822(2),
N1AC11.485(2), P1AN1AC1 129.55(13), N1AP1AS1 116.70(6), S1AP1AC20 112.56(7), S1AP1AC26 114.19(7).
Scheme 3. Syntheses of compounds 8 and 9.
99.43(4)° and Na1AS1ANa1i of 80.57(4)° angels (Table 2). The
Na1AS1 and Na1AS1i bond distances are also almost similar
2.9521(15), and 2.8570(16) Å. Each of the sulfur atoms is l-coordi-
forming a penta-metallacyclo[4.2.0.01,7.02,5.02,4]octane structure.
To the best of our knowledge, this is the first example of such kind
of structural motif in sodium complexes [28].
nated in between the two sodium atoms. Additionally, each
phosphorus atom is coordinated to each sodium atom to form
highly strained three membered metallacycles having P1ANa1
3.1733(14) Å. In complex 7, two additional THF molecules are also
coordinated to each sodium atom and the geometry of each so-
dium atom can be best described as distorted octahedral. The bond
distances Na1AN1 2.381(3), Na1AO1 2.378 (3), and Na1AO2
2.418(3) Å are in the range of the previously reported values. The
whole structure consists four three member rings fused together
The other two dimeric sodium salts [{(THF)2Na(Ph2P(O)
NCPh3)}2] (8) and [{(THF)2Na(Ph2P(S)NCPh3)}{(THF)Na(Ph2P(S)
NCPh3)}] (9) were prepared in a similar fashion involving the reac-
tion of bulky phosphinic amide 4 and phosphinthioic amide 6 with
sodium bis(trimethyl)silyl amide respectively in toluene at room
temperature via the elimination of volatile hexamethyldisilazane
(Scheme 3) [24]. In the solid state, both the complexes 8 and 9
crystallize in triclinic space group P-1 having one molecule (for
8) and two independent molecules in the unit cell (for 9) (Table 1).

194
R.K. Kottalanka et al. / Journal of Molecular Structure 1036 (2013) 188–195
Fig. 2. Solid state structure of compound 7 (a) and 8 (b) omitting hydrogen atoms for clarity. Selected bond lengths [Å] and bond angles[°]: 7; Na1AN1 2.381(3), Na1AP1
3.1733(14), Na1AS1 2.9521(15), Na1AS1i 2.8570(16), Na1AO1 2.378(3), N1AO2 2.418(3), N1AP1 1.593(3), P1AS1 1.9934(12), N1ANa1AP1 29.11(6), N1ANa1AS1 66.87(7),
N1ANa1AS1i 118.37(8), P1ANa1AS1 37.77(3), P1ANa1AS1i 115.24(5), S1ANa1AS1i 99.43(4), N1ANa1AO1 112.89(11), N1ANa1AO2 109.53(10), Na1AP1AS1 77.15(4),
Na1AS1ANa1i 80.57(4), P1ANa1AO1 141.01(9), P1ANa1AO2 98.46(7), S1ANa1AO1 171.28(8), S1ANa1AO2 84.45(7), Na1AS1iAP1i 115.85(5), O1ANa1AO2 87.59(10),
O1ANa1AS1i 88.36(7), O2ANa1AS1i 129.39(8), N1AP1AC1 113.26(14). 8; Na1AN1 2.792(3), Na1AP1 3.0348(17), Na1AO1 2.369(3), Na1AC19 3.086(4), Na1AO1i 2.218(3),
Na1AO2 2.363(3), Na1AO3 2.338(3), Na1AN1AP1 83.20(12), P1AO1 1.520(2), P1AN1 1.564(3), Na1AP1AO1 50.16(10), Na1AO1AP1 100.31(13), N1ANa1AP1 30.79(6),
P1ANa1AO1 29.52(6), Na1AN1AC1 118.3(2), C19ANa1AO1 78.12(10), C19ANa1AO2 82.93(11), C19ANa1AO3 149.33(11), C19ANa1AP1 68.72(8), C19ANa1AN1 57.91(9),
N1ANa1AO1 59.85(9), O1ANa1AO1i 82.70(10), O3ANa1AO1 110.59(11), O2ANa1AO1 160.76(12), O1iANa1AP1 112.19(9), O1iA Na1AC19 107.54(11), O1AP1AN1
114.94(15), Na1AO1ANa1i 97.30(10).
Selected bond lengths and angles are given in Table 2. The sodium
complex 8 is centrosymmetric and dimeric (Fig. 2) in nature where
each sodium atoms are coordinated by two P,P-diphenyl-N-trityl-
phosphinic amido groups via one oxygen, one phosphorus and
one amido nitrogen atom exhibiting a diamond shaped Na2O2 core
with mean O1ANaAO1i of 82.70(10) Å and Na1AO1ANa1i of
97.30(10)° angels. Both the oxygen atoms are bridging coordinated
with two sodium atoms. Besides, each phosphorus atom is coordi-
nated to each sodium atom to form highly strained three mem-
bered metallacycles having P1ANa1 3.0348(17) Å. In complex 8,
two parallel planes containing Na1,O1, P1,N1 and Na1i,O1i,
P1i,N1i atoms are placed at a distance of 0.429 Å and two planes
containing Na1, O1, P1, N1 and Na1, O1, Na1i, O1i make a dihedral
angle of 10.25°. A short contact Naꢃ ꢃ ꢃH between sodium and one of
the phenyl proton (Na1ꢃ ꢃ ꢃC19 (3.086(4) Å and Na1ꢃ ꢃ ꢃH1a 2.598 Å)
is observed which can be attributed as remote or secondary
MACAH interaction [27]. However, in solution all phenyl protons
are appeared equivalent as observed in 1H NMR study presumably
due to dynamic behavior of the complex. Thus in the solid state,
two additional five member metallacycles Na1AN1AC1AC14AC19
and Na1iAN1iAC1iAC14iAC19i are formed. An unusual structural
motif is formed by fusion of four three member and two five mem-
ber metallacycle rings.
Fig. 3. Solid state structure of compound 9 omitting hydrogen atoms for clarity.
Selected bond lengths [Å] and bond angles[°]: Na1AO1 2.271(3), Na1AN1 2.430(2),
Na1AS1 2.7580(15), Na1AS2 2.8498(15), Na1AP1 3.1367(13), Na2AO2 2.299(3),
Na2AN2 2.419(2), Na2AO3 2.535(3), Na2AS2 2.8307(14), Na2AS1 3.1553(16),
Na2AP2 3.1616(13), Na1AC10 3.017(3), O1ANa1AN1 120.41(10), O1ANa1AS1
141.00(10), N1ANa1AS1 68.52(6), O1ANa1AS2 98.54(8), N1ANa1AS2 134.94(8),
S1ANa1AS2 96.02(4), O1ANa1AC10 111.15(11), N1ANa1AC10 60.86(8),
S1ANa1AC10 105.86(7), S2ANa1AC10 85.67(7), O1ANa1AP1, 142.72(8),
N1ANa1AP1 29.73(5), S1ANa1AP1 39.29(2), S2ANa1AP1 118.67(5), C10ANa1AP1
76.08(6), O1ANa1ANa(2) 136.71(8), N1ANa1ANa2 102.78(7), O2ANa2AN2
118.77(10), O2ANa2AO3 90.38(10), N2ANa2AO3 106.30(10), O2ANa2AS2
172.92(8), N2ANa2AS2 68.14(6), O3ANa2AS2 88.87(8), O2ANa2AS1 87.01(8),
N2ANa2AS1 118.34(8), O3ANa2AS1 130.16(8), S2ANa2AS1 88.10(4), O2ANa2AP2
147.99(8), N2ANa2AP2 29.25(5), O3ANa2AP2 100.55(8), S2ANa2AP2 38.89(2),
Unlike compound 8, the sodium complex 9 is noncentrosym-
metric and dimeric and two phosphinthioic amide ligands are
coordinating to two sodium atoms by sulfur, phosphorus and one
amido nitrogen atom exhibiting a diamond shaped Na2S2 core with
mean S1ANaAS1i of S1ANa1AS2 96.02 (4)° and S1ANa2AS2 88.10
(4)° and Na1AS1ANa2 84.96(4)° and Na1AS2ANa2 89.65(4)°
angels. Each of the sulfur atoms is
l-coordinated in between the
two sodium atoms. In addition, each phosphorus atom is coordi-
nated to each sodium atom to form highly strained three
membered
metallacycles
having
P1ANa1
distance
of
S1ANa2AP2
Na1AS1ANa2
107.49(4),
84.96(4),
P1AS1ANa1
P2AS2ANa2
80.56(4),
79.45(4),
P1AS1ANa2
P2AS2ANa1
119.37(5),
128.52(5),
3.1367(13) Å. In complex 9, sodium atom Na2 is attached to two
THF molecules and adopts distorted octahedral geometry whereas
the second sodium atom Na1 is coordinated only with one THF
Na2AS2ANa1 89.65(4), N1AP1AS1 108.69(9), S1AP1ANa1 60.15(4), N2AP2AS2
110.01(9), N2AP2ANa2 48.35(8), S2AP2ANa2 61.66(4).

R.K. Kottalanka et al. / Journal of Molecular Structure 1036 (2013) 188–195
(b) M. Knoerr, C. Strohmann, Organometallics 18 (1999) 248–257;
195
molecule and one phenyl carbon (C10) making a distance of
3.017 Å (Na1ꢃ ꢃ ꢃH 2.649 Å) can be attributed as short MACAH inter-
actions [27]. However, in solution all phenyl protons are equivalent
as observed in 1H NMR spectra. Thus, a five member metallacycle
Na1AN1AC1AC9AC10 is formed and the geometry of Na1 is best
described as distorted tetrahedral. In complex 9, whole structure con-
sists four three membered rings along with one five member ring
(c) P. Braunstein, J. Cossy, M. Knorr, C. Strohmann, P. Vogel, New J. Chem. 23
(1999) 1215–1222.
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fused together forming a hexametallacyclo-[5.4.0.01,5.01,6.08,10.08,11
]
(b) M.W. Avis, C.J. Elsevier, J.M. Ernsting, K. Vrieze, N. Veldman, A.L. Spek, K.V.
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undecane structure (Fig 3). To the best of our knowledge, this kind
of structural motif is not previously described in the literature for
sodium compounds [28]. The three member metallacycles are
highly strained as we can observe from the angles Na1AN1AP1
29.73(5)°, N1AP1AS1 60.15(4)°, P1AS1AN1 80.56(4)° and
S1ANa1AN1 68.52(6)°. Even though the complex 9 is noncentro-
symmetric in the solid state, only one set of signals were recorded
in the 1H, 31P{1H} and 13C{1H} NMR spectra in each case.
(d) P. Imhoff, R. van Asselt, J.M. Ernsting, K. Vrieze, C.J. Elsevier, W.J.J. Smeets,
A.L. Spek, A.P.M. Kentgens, Organometallics 12 (1993) 1523–1536.
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4208.
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2616–2622.
[15] Review R.G. Cavell, R.P. Kamalesh Babu, K. Aparna, J. Organomet. Chem. 617–
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4. Conclusions
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(2001) 4535–4537;
K. Aparna, R.P. Kamalesh Babu, R. McDonald, R.G. Cavell, Angew. Chem., Int. Ed.
40 (2001) 4400–4402.
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(b) K. Aparna, R. McDonald, M. Fuerguson, R.G. Cavell, Organometallics 18
(1999) 4241–4243.
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Inorg. Chim. Acta 303 (2000) 156–162;
In conclusion, we have reported two bulky phosphinamines and
their respective chalcogenides. Using the phsophinamine chalcogenides
three different sodium complexes are prepared where two different
structural motifs of pentametallacyclo-[4.2.0.01,7.02,5.02,4]octane
and hexametalla-cyclo-[5.4.0.01,5.01,6.08,10.08,11]undecane are
observed. The sodium complexes having various structural motifs
can serve as the structural synthon for d- block and f-block metalla-
cycles via salt metathesis reaction. Further reactions with these
ligands are under progress in our laboratory.
(c) A. Recknagel, A. Steiner, M. Noltemeyer, S. Brooker, D. Stalke, F.T. Edelmann,
J. Organomet. Chem. 414 (1991) 327–335;
(d) A. Recknagel, M. Witt, F.T. Edelmann, J. Organomet. Chem. 371 (1989) C40–
C44.
Acknowledgments
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This work was supported by the Department of Science and
Technology India (DST) under the SERC Fast Track Scheme (SR/FT/
CS-74/2010) and start-up grant from IIT Hyderabad. R.K. and K. N.
thanks UGC, India for their PhD fellowship. Generous support from
K. Mashima, Osaka University, Japan is gratefully acknowledged.
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