Late transition metal complexes derived from diphosphazane monosulfide ligands: X-ray crystal structures of [Ru3(μ-CO)(CO)7-(μ3-S) {Ph2PN((S)-*CHMePh)PPh2- κ2P,P}] and [Rh(CO)Cl{Ph2</s

Article abstract of DOI:10.1016/S0022-328X(02)02220-9

The oxidative addition reactions of diphosphazane monosulfides, Ph₂PN(R)P(S)Ph₂ (R=(S)^-*CHMePh (1), CHMe₂ (2)) with [Ru₃(CO)₁₂] afford sulfur-monocapped triruthenium clusters of the type PP

Full text of DOI:10.1016/S0022-328X(02)02220-9

Journal of Organometallic Chemistry 669 (2003) 79Á86
/
www.elsevier.com/locate/jorganchem
Late transition metal complexes derived from diphosphazane
monosulfide ligands: X-ray crystal structures of [Ru3(m-CO)(CO)7-
(m3-S){Ph2PN((S)-*CHMePh)PPh2-k2P,P}] and
[Rh(CO)Cl{Ph2PN((S)-*CHMePh)P(S)Ph2}-k2P,S]
Part 16. Organometallic chemistry of diphosphazanesꢀ
Kannan Raghuraman, Setharampattu S. Krishnamurthy *, Munirathinam Nethaji
Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560 012, India
Received 8 July 2002; received in revised form 5 December 2002; accepted 16 December 2002
Abstract
The oxidative addition reactions of diphosphazane monosulfides, Ph2PN(R)P(S)Ph2 (Rꢀ
/
(S)-*CHMePh (1), CHMe2 (2)) with
[Ru3(CO)12] afford sulfur-monocapped triruthenium clusters of the type [Ru3(m-CO)(CO)7(m3-S){Ph2PN(R)PPh2-k2P,P}] (Rꢀ
/
(S)-
*CHMePh (3), CHMe2 (4)); the X-ray crystal structure of 3 reveals the chelating mode of coordination of the diphosphazane ligand,
which is rarely observed for such type of complexes. The bridge-splitting reactions of 1 and 2 with [{Rh(m-Cl)(CO)2}2] yield
[Rh(CO)Cl{Ph2PN(R)P(S)Ph2-k2P,S}] (Rꢀ
/
(S)-*CHMePh (5), CHMe2 (6)); the X-ray crystal structure of 5 confirms that the ‘CO’
S bond. The reactions of [MCl2(COD)] with 1 and 2 yield chelate complexes, [MCl2{Ph2PN(R)P(S)Ph2-
Pd (7 and 8) or Pt (9 and 10)].
ligand is trans to the PÄ
/
k2P,S}] [Mꢀ
/
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Chiral phosphorus ligands; Cluster compounds; Organometallic compounds; P,S-donor ligands
1. Introduction
coordination chemistry [5Á
work on the organometallic chemistry of diphosphazane
type ligands [9Á11], herein we report the reactions of
diphosphazane monosulfides, Ph2PN(R)P(S)Ph2 (Rꢀ
(S)-*CHMePh (1) or CHMe2 (2)) with [Ru3(CO)12],
[{Rh(m-Cl)(CO)2}2] and [MCl2(1,5-COD)] (MꢀPd, Pt)
(1,5-CODꢀ1,5-cyclooctadiene). The molecular struc-
/
8]. In continuation of our
Heterofunctional ligands containing soft and hard
donor sites have attracted considerable attention as they
are expected to generate transition metal complexes,
which are efficient for various catalytic transformations
/
/
/
[1Á4]. Transition metal complexes bearing P,S-donor
/
/
ligands have been used as catalysts for hydroformyla-
tion [2,3] and hydrogenation [4] reactions. Heterofunc-
tional diphosphazanes of the type X2PN(R)P(E)X2
containing phosphorus and other donor atoms such as
sulfur, oxygen or nitrogen would display interesting
tures of the complexes [Ru3(m-CO)(CO)7(m3-S){Ph2PN-
(R)PPh2-k2P,P}]
(R)P(S)Ph2-k2P,S}] (5) (Rꢀ
(3)
and
[Rh(CO)Cl{Ph2PN-
(S)-*CHMePh) have been
/
confirmed by single crystal X-ray diffraction. A part of
this work has appeared in a Conference Proceedings
[11]. The synthesis of chiral diphosphazane monosulfide
(1) and its reactions with Rh(I), Rh(III) and Ir(III)
complexes were reported while this manuscript was
under preparation [12].
ꢀ For Part 15, see Ref. [10d].
* Corresponding author. Fax: ꢁ
/
91-80-3600-683.
E-mail address: sskrish@ipc.iisc.ernet.in (S.S. Krishnamurthy).
0022-328X/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(02)02220-9

80
K. Raghuraman et al. / Journal of Organometallic Chemistry 669 (2003) 79Á86
/
2. Experimental
7.8Á
0.99 (d, JHH
(CDCl3, ppm): 63.8 (s).
Complex 4: m.p. 195Á
C35H27NO8P2Ru3S: C, 42.6; H, 2.8; N, 1.4. Found:
43.1; H, 2.8; N, 1.3%. IR (n(CÅ
O), cmꢃ1): 2047m,
2009s, 1962m, 1940sh, 1813m. H-NMR (CDCl3, ppm):
7.6Á6.5 (m, aryl protons), 3.90 (m, CHÁCHMe2), 0.87
CHMe2). 31P-NMR (CDCl3,
/
6.4 (m, aryl protons), 4.32 (m, CHÁ
/
*CHMePh),
3
ꢀ
/
7.1 Hz, CH3Á
/
*CHMePh). 31P-NMR
2.1. General procedures
/
200 8C. Anal. Calc. for
All the reactions and manipulations were carried out
under an inert atmosphere of argon using standard
Schlenk techniques. The solvents were purified and
distilled under argon prior to use. Infrared spectra
were recorded on a Bruker FTIR spectrometer using
/
1
/
/
3
(d, JHH
ꢀ
/
7.1 Hz, CH3Á
/
thin film samples in KBr disc. The H- and 31P-NMR
ppm): 72.4 (s).
1
spectra were recorded on a Bruker ACF-200 spectro-
meter in CDCl3 solutions at 25 8C using Me4Si or 85%
H3PO4 (ext) as reference standards, respectively. The
diphosphazane monosulfide (2) [5], [{Rh(m-Cl)(CO)2}2]
2.4. Synthesis of cis-[Rh(CO)Cl{Ph2PN(R)P(S)Ph2-
k2P,S}] [Rꢀ
(S)-*CHMePh (5), CHMe2 (6)]
/
[13], [MCl2(COD)] [Mꢀ
sized by published procedures. [Ru3(CO)12] (Strem) and
Me3NO×2H2O (Aldrich) were used as received.
/
Pd(II), Pt(II)] [14] were synthe-
A mixture of [{Rh(m-Cl)(CO)2}2] (0.050 g, 1.28ꢂ
10ꢃ4 mol) and Ph2PN(R)P(S)Ph2 (0.133g for Rꢀ
(S)-
*CHMePh, 0.117g for RꢀCHMe2, 2.56ꢂ
10ꢃ4 mol)
/
/
/
/
/
was dissolved in 20 ml of benzene. The mixture was
stirred for 2 h and concentrated in vacuo to 5 ml. Petrol
(5 ml) was added and the solution kept at 25 8C for 12 h
to obtain the title complexes as yellow crystals (yield
2.2. Synthesis of Ph2PN(R)P(S)Ph2 (Rꢀ
*CHMePh (1))
/
(S)-
Elemental sulfur (0.033 g, 1.02ꢂ
/
10ꢃ3 mol) was
80Á85%).
/
added to a solution of the diphosphazane, Ph2PN((S)-
*CHMePh)PPh2 [10] (0.50 g, 1.02ꢂ
10ꢃ3 mol) in
benzene (30 ml). The mixture was heated under reflux
for 2 h, concentrated in vacuo to ꢀ15 ml, and kept at
25 8C for 12 h to yield the diphosphazane monosulfide
(1) as colorless crystals in 85Á90% yield. If the con-
Complex 5: m.p. 186 8C. Anal. Calc. for
C33ClH29NOP2RhS: C 57.6, H 4.2, N 2.0% Found: C
57.5, H 4.3, N 2.2%. IR (cmꢃ1): 1985s, 1432m, 1099s,
/
/
1
1014m, 937m, 870s, 749s, 695s, 591m, 522m, 495m. H-
NMR (CDCl3, ppm): 8.4 Á
(m, CHÁ*CHMePh), 1.20 (d, JHH
*CHMePh).
/
6.3 (m, aryl protons), 5.10
/
3
/
ꢀ
/
7.1 Hz, CH3Á
/
centrated solution did not give crystals of 1 after a day, a
flash column chromatography on a silica gel column
Complex 6: m.p. 194 8C. Anal. Calc. for
C28ClH27NOP2RhS: C 53.7, H 4.4, N 2.2% Found: C
53.6, H 4.4, N 2.3%. IR (cmꢃ1): 1981s, 1435m, 1170w,
1100s, 1026w, 979s, 898s, 840s, 747m, 693m, 578m,
using petrolÁ
formed to yield 1 in a pure form (yield 70%). M.p. 170Á
172 8C (lit. [12] 172Á174 8C); Anal. Calc. for
C32H29NP2S: C, 73.7; H, 5.6; N, 2.7. Found: C, 73.9;
H, 5.6; N, 2.4%. 1H-NMR (CDCl3, ppm): 7.77Á
7.06 (m,
aryl protons), 5.17 (m, CHÁ*CHMePh), 1.82 (d,
3JHH
7.0 Hz, CH3Á*CHMePh).
/ethylacetate (9:1 v/v) as eluant was per-
/
/
560m, 518m, 498m, 444m 1H-NMR (CDCl3, ppm): 8.0Á
/
/
7.3 (m, aryl protons), 4.00 (m, CHÁ
/
CHMe2), 0.60 (d,
/
3JHH
ꢀ
/
7.1 Hz, CH3ÁCHMe2).
/
ꢀ
/
/
2.3. Synthesis of [Ru3(m-CO)(CO)7(m3-
S){Ph2PN(R)PPh2-k2P,P}] [Rꢀ
(S)-*CHMePh (3)
or CHMe2 (4)]
2.5. Synthesis of [MCl2{Ph2PN(R)P(S)Ph2-k2P,S}]
(MꢀPd, Pt) (7Á10)
/
/
/
A mixture of [MCl2(COD)] (Mꢀ
for MꢀPd, 0.075 g for Mꢀ
Ph2PN(R)P(S)Ph2 (0.104 g for Rꢀ
0.091 g for RꢀCHMe2, 2.00ꢂ
10ꢃ4 mol) was dissolved
in CH2Cl2 (10 ml) and the solution stirred at 25 8C for 1
h. Evaporation of the solvent in vacuo yielded an oily
residue which was washed twice with hot petrol to
/
Pd or Pt) (0.057 g
A mixture of [Ru3(CO)12] (0.050 g, 7.82ꢂ
Ph2PN(R)P(S)Ph2 (0.041 g for Rꢀ(S)-*CHMePh,
0.036 for RꢀCHMe2, 7.82ꢂ
10ꢃ5 mol) and
Me3NO×2H2O (0.006 g, 8.60ꢂ
10ꢃ5 mol) was dissolved
in toluene (20 ml). The solution was heated under reflux
for 1 h. The resulting dark red solution was evaporated
to dryness and the residue dissolved in CH2Cl2 (2 ml).
The title complexes were isolated by preparative TLC on
/
10ꢃ5 mol),
/
/
Pt, 2.00ꢂ
/
10ꢃ4 mol) and
/
/
(S)-*CHMePh,
g
/
/
/
/
/
/
remove cyclooctadiene and crystallised from CH2Cl2Á
petrol (1:3) mixture to yield the title complexes (yield
80Á85%).
[PdCl2{Ph2PN(*CHMePh)P(S)Ph2Á
/
silica, using CH2Cl2Á
0.9). (yield 25Á30%).
Complex 3: m.p. 186Á
C40H29NO8P2Ru3S: C, 45.8; H, 2.8; N, 1.3. Found: C,
45.7; H, 2.8; N, 1.3%. IR (n(CÅ
O), cmꢃ1): 2058s,
2015vs, 1984s, 1878m 1814w. H-NMR (CDCl3, ppm):
/petrol (1:1) as eluant (red band; Rf
/
/
/
k2P,S}] (7): m.p.
/
188 8C. Anal. Calc. for
205 8C. Anal. Calc. for C32Cl2H29NP2PdS: C, 54.9; H,
4.2; N 2.0. Found: C, 54.2; H, 4.2; N, 2.1%. IR (cmꢃ1):
1437s, 1102s, 1013m, 935m, 875m, 769m, 746s, 691s. 1H-
/
1
NMR (CDCl3, ppm): 8.1Á6.1 (m, aryl protons), 4.94 (m,
/

K. Raghuraman et al. / Journal of Organometallic Chemistry 669 (2003) 79Á
/86
81
3
*CHMePh), 1.17 (d, JHH
CHÁ
/
ꢀ
/
7.1 Hz, CH3Á
/
3.1. Reactions of Ph2PN(R)P(S)Ph2 with
[Ru3(CO)12]
*CHMePh).
[PdCl2{Ph2PN(CHMe2)P(S)Ph2-k2P,S}] (8): m.p.
212 8C. Anal. Calc. for C27Cl2H27NP2PdS: C, 50.9; H,
4.3; N, 2.2. Found: C, 49.7; H, 4.2; N, 2.1%. IR (cmꢃ1):
1436s, 1100s, 1012s, 933m, 874m, 769m, 746s, 689s. 1H-
The oxidative addition reactions of diphosphazane
monosulfides Ph2PN(R)P(S)Ph2 {Rꢀ(S)-*CHMePh
/
(1), CHMe2 (2)} with [Ru3(CO)12] in toluene at 105 8C
in the presence of Me3NO afford sulfur-mono capped
triruthenium clusters, [Ru3(m-CO)(CO)7(m3-S){Ph2PN-
NMR (CDCl3, ppm): 8.2Á6.8 (m, aryl protons), 4.42 (m,
/
3
CHÁ
/
CHMe2), 1.24 (d, JHH
ꢀ
/
7.0 Hz, CH3ÁCHMe2).
/
[PtCl2{Ph2PN(*CHMePh)P(S)Ph2-k2P,S}] (9): m.p.
218 8C. Anal. Calc. for C32Cl2H29NP2PtS: C, 48.8; H,
3.7; N, 1.8. Found: C, 48.6; H, 3.8; N, 1.6%. IR (cmꢃ1):
(R)PPh2-k2P,P}] {Rꢀ
/
(S)-*CHMePh (3), or CHMe2
(4)} (Scheme 1). These complexes could be isolated in a
pure form by preparative TLC, but their yields are low
owing to the formation of several other products, which
could not be characterized. The structures of 3 and 4
have been elucidated by IR and NMR spectroscopic
techniques. The IR spectra indicate the presence of both
terminal and bridging carbonyl ligands. The molecular
structure of 3 has been established by single crystal X-
ray diffraction. Complex 4 is assigned an analogous
structure because its spectroscopic features are very
similar to those of 3 (see Section 2 for IR and NMR
data). It may be noted that the phosphorus-31 chemical
shifts for 4 and 5 lie downfield from those of the
1437s, 1103s, 1031m, 1013w, 935m, 875m, 811m, 772m,
1
745s, 689s. H-NMR (CDCl3, ppm): 8.4Á
/
6.1 (m, aryl
7.0
protons), 5.30 (m, CHÁ
/
*CHMePh), 1.17 (d,3JHH
ꢀ
/
Hz, CH3Á
/
*CHMePh).
[PtCl2{Ph2PN(CHMe2)P(S)Ph2-k2P,S}] (10): m.p.
193 8C. Anal. Calc. for C27Cl2H27NP2PtS: C, 44.7; H,
3.8; N, 1.9. Found: C, 44.3; H, 3.7; N, 1.9%. H-NMR
1
(CDCl3, ppm): 8.1Á
/
6.8 (m, aryl protons), 4.38 (m, CHÁ
/
3
CHMe2), 1.17 (d, JHH
ꢀ
/
7.0 Hz, CH3ÁCHMe2).
/
respective free ligands, Ph2PN(R)PPh2 (Rꢀ(S)-
/
2.6. X-ray diffraction study of 3 and 5
*CHMePh, CHMe2) (Table 1). On the other hand,
there is a significant upfield shift of the methyl proton
resonances in the metal clusters relative to those for the
Crystals of 3 and 5 suitable for X-ray analysis were
grown by slow evaporation of a toluene solution and
free ligands. The values of [Dd(CH3)ꢀ
/
d (complex)ꢃd
/
dichloromethaneÁpetrol (1:1) solutions, respectively. A
/
(ligand)] for complexes 3 and 4 are 0.79 and 0.23,
respectively [10c]. It is also worth noting that the
downfield shifts of the 31P resonance observed for the
chelate complexes 3 and 4 are much less than the similar
downfield shifts observed for the dichalcogenide capped
triruthenium clusters, [Ru3(m3-S)2(CO)7(m-(Ph2P)2NH)]
in which the diphosphazane acts as a bridging ligand
[15]. The reaction of Ru3(CO)12 with the chiral ligand 1
using the benzophenone-ketyl induced CO substitution
method also gives the chelate cluster 3 as the only
product as shown by 31P-NMR spectrum of the reaction
mixture. Oxidative sulfur transfer occurs even under
these conditions.
suitable crystal for X-ray analysis was glued to a glass
fiber and coated with paraffin oil to protect it from
atmospheric air and moisture during data collection.
Cell constants were obtained by least-squares refinement
of the setting angles of 25 reflections in the range 16B
/
2u B308. The intensity data collection was monitored
/
for any variations by three repeatedly measured control
reflections. Lorentz and polarization corrections were
applied to the intensity data. The structure was solved
by Patterson methods using SHELXS-86 (G.M. Sheldrick,
Universitat Gottingen, 1990) and refined by full-matrix
¨
¨
methods against the Fo2 data employing SHELXL-93
(G.M. Sheldrick, Universitat Gottingen, 1993) program;
¨
¨
Predieri and coworkers have demonstrated that the
reactions of [Ru3(CO)12] with diphosphinoalkane dis-
the hydrogen atoms were allowed to ride on the attached
atoms during refinements.
elenides, Ph2P(Se)(CH2)nP(Se)Ph2 (nꢀ1 or 2) give
/
diselenido bicapped trinuclear clusters of the type
[Ru3(m3-Se)2(CO)7{m-(Ph2P)2(CH2)n}] as the main pro-
ducts.
A
tetranuclear cluster [Ru4(m4-Se)2(m-CO)-
3. Results and discussion
(CO)8{m-(Ph2P)2CH2}] and the cubane-like cluster
[Ru4(m4-Se)4(CO)10{m-(Ph2P)2CH2}] have also been iso-
lated from the reaction of [Ru3(CO)12] with Ph2P(Se)-
(CH2)P(Se)Ph2. In all these cases, the diphosphane
The synthesis of the diphosphazane monosulfide,
Ph2PN(R)P(S)Ph2 (RꢀCHMe2) (2) was reported from
/
our laboratory previously [5]. We now report the
preparation of the chiral analogue, Ph2PN(R)P(S)Ph2
functions as a bridging ligand [16Á18]. Only in the
/
case of 1,1 bis(diphenylphosphino)ferrocene diselenide
(dppfSe2), have two isomeric nido-clusters [Ru3(m3-
Se)2(dppf)(CO)7] which contain dppf as a chelating or
a bridging ligand been isolated and structurally char-
acterized [18,19].
(Rꢀ(S)-*CHMePh) (1) by a similar procedure using
/
benzene as the solvent. The yield of 1 is higher than that
reported very recently by Simon-Manso et al. [12], who
used diethyl ether as the solvent for the reaction.

82
K. Raghuraman et al. / Journal of Organometallic Chemistry 669 (2003) 79Á86
/
Scheme 1. Reactions of Ph2PN(R)P(S)Ph2 with [Ru3(CO)12], [{Rh(m-Cl)(CO)2}2] and [MCl2(COD)] (MꢀPd or Pt).
/
The reactions of Ru3(CO)12 with diphosphazane
dichalcogenides, Ph2P(E)NHP(E)Ph2 (EꢀS or Se)
3.2. Reactions of Ph2PN(R)P(S)Ph2 with [{Rh(m-
Cl)(CO)2}2] and [MCl2(COD)] [MꢀPd or Pt]
/
/
(dppaE2) in the presence of Me3NO afford diselenido
bicapped tetranuclear clusters, [Ru4(m4-E)2(m-CO)-
(CO)8{m-(Ph2P)2NH}] and a trinuclear cluster, [Ru3-
(m3-S)2(CO)7{m-(Ph2P)2NH}], in which the dppa ligand
bridges two ruthenium centers. The formation of a
bicapped sulfido triruthenium cluster, [Ru3(m3-
S)2(CO)7{(Ph2P)2NH}] bearing a chelated dppa has
been inferred from spectroscopic data [15]. Complexes
3 and 4 represent a new type of structural motif (see
below) in mono chalcogenido capped triruthenium
carbonyl clusters in that they contain a chelating
diphosphazane ligand. They belong to the family of
The reactions of two equivalents of diphosphazane
monosulfides, Ph2PN(R)P(S)Ph2 [Rꢀ(S)-*CHMePh
/
(1), CHMe2 (2)] with one equivalent of [{Rh(m-Cl)-
(CO)2}2] give [Rh(CO)Cl{Ph2PN(R)P(S)Ph2-k2P,S}]
[Rꢀ(S)-*CHMePh (5), CHMe2 (6)] in good yields
/
(Scheme 1). These yellow-colored complexes (5 and 6)
are stable in a wide range of organic solvents and are
characterized by spectroscopic and analytical techniques
(see Section 2 and Table 1). The molecular structure of
complex 5 is confirmed by a single crystal X-ray
diffraction study.
Reactions of [MCl2(COD)] (Mꢀ
molar proportions of Ph2PN(R)P(S)Ph2 {Rꢀ
/
Pd, Pt) with 1:1
(S)-
clusters of the type, [M3(m3-E)(L)10] (Eꢀ
/
S or Se; Lꢀ
/
/
two-electron donor ligand) [20].
Table 1
31P{1H}-NMR spectral data of transition metal complexes of diphosphazane monosulfides
a
Compound
Chemical shift (ppm)
2JPP (Hz)
b
b
dPPh2
DPPh2
dP(S)Ph2
DP(S)Ph2
1 (L1)
51.5 (br, s)
54.4 (d)
Á
Á/
/
71.3 (d)
67.5 (d)
68.5 (d)
69.2 (d)
72.6 (d)
75.2 (d)
71.5 (d)
71.6 (d)
Á
Á/
/
14.6
63.0
c
2 (L2)
[Rh(CO){k2-L1}Cl] (5)
[Rh(CO){k2-L2}Cl] (6)
[PdCl2{k2-L1}] (7)
[PdCl2{k2-L2}] (8)
[PtCl2{k2-L1}] (9)
112.3 (dd)
114.9 (dd)
94.8 (d)
60.8
60.0
43.3
42.9
17.5
15.2
ꢃ
/
2.8
1.7
1.3
7.7
0.3
4.1
63.0
65.0
d
e
49.0
51.0
97.3 (d)
69.0 (d)
69.6 (d)
f
46.8
47.7
[PtCl2{k2-L2}] (10)
g
a
Recorded at 81 or 162 MHz in CDCl3.
b
Dꢀ
/
d (complex)ꢃd (ligand).
/
c
d
e
f
Data from Ref. [5].
1JRh Á P 167.0 Hz.
1JRh Á P 164 Hz.
2
1JPt Á P 3794, JPt Á P(s) 105.8 Hz.
g
2
1JPt Á P 3787 Hz, JPt Á P(S) 99.5 Hz.

K. Raghuraman et al. / Journal of Organometallic Chemistry 669 (2003) 79Á
/86
83
2
*CHMePh 1, CHMe2 2} in dichloromethane at ambient
temperature give the chelate complexes [MCl2{Ph2PN-
The JPP value for N-isopropyl diphosphazane mono-
sulfide (2) is much larger than that for the N-(S)-
*CHMePh diphosphazane monosulfide (1) but irrespec-
(R)P(S)Ph2-k2P,S}] [Mꢀ
RꢀCHMe2 (8); Mꢀ
CHMe2 (10)]. The structure of complexes 7Á
/
Pd, Rꢀ
Pt, Rꢀ(S)-*CHMePh (9), Rꢀ
10 have
/
(S)-*CHMePh (7),
2
/
/
/
/
tive of the substituent on the nitrogen, the JPÁP values
for the complexes of a particular metal show only small
/
been assigned on the basis of NMR data (see Section 2
and Table 1).
variations (1Á2 Hz) presumably because of the freezing
of the ligand conformation upon complex formation [7].
/
3.3. Phosphorus-31-NMR data
3.4. Molecular structure of 3
The 31P-NMR data for the ligands 1 and 2 and their
complexes are listed in Table 1. The chemical shifts of
the PPh2 phosphorus (PIII centers) are substantially
shifted to a lower field compared to those of the free
ligands. The pronounced deshielding of PIII is probably
due to the chelate ring stabilizing effect and is in
agreement with a similar trend observed for metal
complexes of diphosphazane monosulfide ligands [7].
The coordination shift of the P(S)Ph2 phosphorus is
The molecular structure of 3, determined by a single
crystal X-ray diffraction study, is shown in Fig. 1. The
structure represents a 48-electron triruthenium cluster
framework that contains a chelated chiral diphospha-
zane ligand. The space group has been identified as P21;
there are two crystallographically independent mole-
cules in the unit cell. Crystallographic information and
salient bond lengths and bond angles are given in Tables
2 and 3. There are no significant differences between the
bonding parameters of the two molecules. The torsion
angles around the chiral carbon atom in both the
molecules (molecules 1 and 2) do, however, differ. The
two molecules can be regarded as rotamers arising from
generally very small (ꢃ
/
2.8 to ꢁ4.1 ppm); evidently, the
/
coordination of the chalcogen atom in these complexes
does not confer any extraordinary chelate ring effect for
the chalcogen- bearing phosphorus as compared to the
trivalent phosphorus directly bound to the metal center.
rotation around the NÁC bond. The structure of 3
/
Fig. 1. A view of the molecular structure of [Ru3(m3 Á
/
S)(m-CO)(CO)7{Ph2PN((S)-*CHMePh)PPh2-k2P,P}] (3) (molecule 1 only shown) with the
atomic labeling scheme.

84
K. Raghuraman et al. / Journal of Organometallic Chemistry 669 (2003) 79Á86
/
Table 2
X-ray crystallographic data and structure refinements for 3 and 5
Table 3
Selected bond lengths (A) and bond angles (8) for complexes 3 and 5
˚
3
5
Compound 3
Compound 5
Empirical formula
C
40H29NO8-
C33H29ClNO-
P2RhS
Bond lengths
P2Ru3S
1048.85
293(2)
Ru(11)Á
Ru(11)Á
Ru(11)Á
Ru(11)Á
Ru(11)Á
Ru(11)Á
Ru(11)Á
Ru(12)Á
Ru(12)Á
Ru(12)Á
Ru(12)Á
Ru(12)Á
Ru(12)Á
Ru(13)Á
Ru(13)Á
Ru(13)Á
Ru(13)Á
P(11)Á
/
Ru(12)
Ru(13)
S(1)
2.815(2) Rh(1)Á
2.733(2) Rh(1)Á
2.366(5) Rh(1)Á
2.357(5) Rh(1)Á
2.344(4) C(1)Á
/
C(1)
P(12)
S(1)
1.79(2)
2.208(5)
2.369(5)
2.382(5)
1.15(3)
1.992(5)
1.70(1)
1.74(1)
Formula weight
Temperature (K)
˚
Wavelength (A)
687.02
293(2)
/
/
/
/
0.71070
Monoclinic
P21
0.71070
Monoclinic
P21
/P(11)
/Cl(1)
Crystal system
Space group
Unit cell dimensions
/P(12)
/
O(1)
P(11)
P(11)ÁN(1)
P(12)
/
C(133)
C(134)
Ru(13)
S(1)
1.82(2)
1.94(2)
S(1)Á
/
/
/
˚
a (A)
12.183(4)
25.100(18)
14.043(4)
108.49(2)
4073(3)
4
13.421(4)
14.9810(10)
15.477(5)
95.39(3)
3098(1)
4
/
2.711(2) N(1)Á
/
˚
b (A)
/
2.341(5)
2.47(2)
1.90(2)
1.87(3)
1.94(2)
2.344(5)
1.84(2)
1.93(3)
1.94(2)
1.71(1)
˚
c (A)
/
C(134)
C(135)
C(136)
C(137)
S(1)
b (8)
/
3
˚
V (A )
/
Z
/
Dcalc (Mg mꢃ3
)
1.711
1.251
1.473
0.825
/
Absorption coefficient (mmꢃ1
F(000)
)
/
C(138)
C(139)
C(140)
2036
1400
/
Crystal size (mm3)
0.35ꢂ
0.275
u range for data collection (8) 1.53Á
/0.30ꢂ
/
0.57ꢂ
0.35
1.32Á
05h 5
05k 5
185l 5
/
0.42ꢂ
/
/
/
N(11)
/
24.98
h 514,
k 529,
165l 515
/
24.96
15,
17,
18
Bond angles
P(12)ÁN(11)Á
Ru(13)ÁRu(11)Á
Ru(12)ÁRu(13)Á
Ru(12)Á
Ru(12)Á
Ru(13)Á
P(12)ÁRu(11)Á
Index ranges
05
05
ꢃ
7592
7340
[Rint
/
/
/
/
/
/
P(11)
Ru(12)
Ru(11)
101.7(7) P(11)Á
58.5(1) C(1)ÁRh(1)Á
62.3(1) P(12)ÁRh(1)Á
70.7(1) C(1)ÁRh(1)ÁCl(1)
73.5(1) P(12)ÁRh(1)Á
71.0(1) S(1)ÁRh(1)ÁCl(1)
68.1(2) O(1)ÁC(1)ÁRh(1)
/
N(1)Á
/
P(12)
P(12)
S(1)
110.1(8)
92.8(7)
89.2(2)
87.5(7)
/
/
/
/
/
/
/
/
/
/
/
ꢃ/
/
/
/
/
/
/
Reflections collected
Independent reflections
5960
5656
[Rint
/
S(1)Á
S(1)Á
S(1)Á
/
Ru(13)
Ru(11)
Ru(11)
/
/
/
/
/
/
Cl(1) 172.9(2)
ꢀ/
0.0593]
ꢀ/0.0261]
/
/
/
/
90.0(2)
Refinement method
Full-matrix least- Full-matrix least-
/
/P(11)
/
/
169.5(2)
squares on F2
7337/1/991
1.038
squares on F2
5656/1/721
0.960
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I ꢁ
/
2s(I)]
R1ꢀ
wR2ꢀ
R1ꢀ0.0792,
wR2ꢀ0.1764
0.02(8)
2.301 and
1.478
/
0.0617,
R1ꢀ
wR2ꢀ
R1ꢀ0.0668,
wR2ꢀ0.1570
0.02(8)
1.172 and
0.966
/
0.0509,
ligand [22]. Of the seven terminal carbonyl lignads, the
two ruthenium centers Ru12 and Ru13 each carry three
terminal carbonyl ligands while one terminal carbonyl is
attached to Ru11. There is one ‘bent semi-bridging’
carbonyl [23] between Ru11 and Ru12 which forms the
/0.1586
/
0.1363
R indices (all data)
/
/
/
/
Absolute structure parameter
Largest difference peak and
ꢃ
/
ꢃ
/
ꢃ3
˚
hole (e A
)
ꢃ/
ꢃ/
largest side of the ruthenium triangle; the Ru12Á
/
C134
˚
distance (2.47(2) A) is longer than the Ru11Á
/
C134
˚
distance (1.94(2) A).
displays a tetrahedral Ru3S core in which an isosceles
triangle of ruthenium atoms is almost symmetrically
The crystal packing diagram shows an interesting
helical arrangement of molecules in the crystal lattice
(see Fig. B of Section 5). The helical array, formed by
two independent molecules (molecules 1 and 2), consists
of two strands which run parallel to each other. Each
strand consists of molecules 1 and 2 packed one over the
other. Both intra- and intermolecular hydrogen bonding
provide the major source of stability. The helical arrays
are connected by hydrogen-bonds; within each strand,
molecules 1 and 2 are also connected by hydrogen
bonds. The phenyl hydrogen atoms in the diphospha-
zane ligand act as hydrogen-bond donors and the
oxygen atoms of the carbonyl ligands and sulfur atoms
capped by a sulfur atom. The Ru11Á
/
Ru13 and Ru12Á
/
Ru13 bonds are of comparable length (2.733(2) and
˚
2.711(2) A) while Ru11Á
(2.815(2) A). The first two RuÁRu distances are
/
Ru12 bond is slightly longer
˚
/
significantly shorter than those found in the selenium
monocapped cluster [Ru3(m3-Se)(m3-CO)(CO)7(PPh3)2]
[20] and the unsubstituted sulfur monocapped cluster
[Ru3(m3-S)(m3-CO)(CO)9] [21]. The RuÁ
/
S bonds lie in
2.367 A and are comparable to those
found in other sulfur capped triruthenium clus-
ters[15,21]. The RuÁP distances are unexceptional. The
mean PÁN bond distance (1.70(1) A) is almost the same
as that found in the free ligand Ph2PN(CHMePh)PPh2
˚
the range 2.341Á
/
/
˚
/
act as hydrogen-bond acceptors. The CÁ
tances and CÁ
HÁ Á ÁO angles lie in the range 3.19Á
and 124Á1678, respectively. The CÁ
HÁ Á ÁS distances and
CÁ
HÁ Á ÁS angles are in the range 3.46Á
1568 (see Fig. C and Table C of Section 5).
/
HÁ Á ÁO dis-
˚
/
/
3.85 A
˚
(mean PÁ
the chelate formation, the PÁ
narrowed to 101.78 as compared to that in the free
/N distance 1.719(1) A). However as a result of
/
/
˚
/
NÁP angle is considerably
/
/
/
3.74 A and 145Á
/

K. Raghuraman et al. / Journal of Organometallic Chemistry 669 (2003) 79Á
/86
85
3.5. Molecular structure of 5
PÁ
/
RhÁ
/
Cl and the RhÁ
/
CÁ/O bond angles are more
linear in the dppmS complex (177.7 and 179.48, respec-
tively) compared to the corresponding values in 5 (173
The structure of 5 has been confirmed by single
crystal X-ray diffraction. The space group is identified
as P21. The unit cell contains two crystallographically
independent molecules. An ORTEP view of one of the
molecule is shown in Fig. 2. Crystallographic informa-
tion and the important bond lengths and bond angles
are listed in Tables 2 and 3. Except the torsion angles
around the chiral carbon atom, there are no significant
differences in the bond lengths and bond angles of the
two molecules.
and 1708). The PÁ
/
N bond distances [1.74(1) and 1.70(1)
˚
A] do not vary significantly from those observed for the
˚
free ligand [1.749(4) and 1.695 (4) A] [12] but the PÁS
/
˚
bond distance [1.992(5) A] increases by 0.04 A [1.955(2)
˚
for free ligand]. Upon complexation the PÁNÁP bond
/
/
angle [110.1(8)8] shows an appreciable decrease from
that [124.3(2)8] for the free ligand; nevertheless, the
geometry around the nitrogen atom is planar. An
examination of the packing diagram and of intermole-
cular contacts of 5 shows that there are intermolecular
hydrogen bonds between the hydrogen atoms of the
phenyl groups and the chloride or the carbonyl oxygen
The molecule has a square-planar geometry around
rhodium, with the sulfur atom trans to carbon mon-
oxide. The carbonyl ligand is slightly bent about the
of the neighboring molecule. The CÁ
and CÁ
HÁ Á ÁO angles are in the range 3.18Á
133Á1658, respectively, the CÁ
HÁ Á ÁCl distances and CÁ
/
/
HÁ Á ÁO distances
˚
/
carbon atom with a Rh1Á
Cl1ÁRh1ÁP12 angle of 172.9(2)8 shows that there is a
slight shift from an idealised square planar geometry.
The slightly large bond angle of 92.8(7)8 for P12ÁRh1Á
/
C1Á
/
O1 angle of 170(2)8. The
/
3.55 A and
/
/
/
/
/
˚
HÁ Á ÁCl angles are in the range 3.50Á
/
3.82 A and 127Á
/
/
1518 respectively (see Table E of the Section 5).
C1 is probably due to steric repulsion of the phenyl
group of the diphosphazane with the carbonyl group.
This results in a slight decrease of C1Á
[87.5(7)8] from the ideal value of 908. The angles S1Á
Rh1ÁCl1 [90.0(2)8] and S1ÁRh1ÁP12 [89.2(2)8] are close
to 908. The RhÁP and RhÁC1 distances in complex 5
are comparable to those observed for the bis(diphenyl-
phosphino)methane monosulfide (dppmS) complex, cis-
[Rh(CO)Cl{Ph2PCH2P(S)Ph2-k2P,S}] [3]. However, the
/
Rh1Á
/
Cl1 angle of
/
4. Conclusions
/
/
/
/
/
The present study demonstrates that the oxidative
chalcogen transfer reactions of diphosphazane mono-
chalcogenides with [Ru3(CO)12] may proceed by a
different pathway from that observed for the analogous
Fig. 2. A view of the molecular structure of [RhCl(CO){Ph2PN{((S)-*CHMePh) P(S)Ph2-k2P,S}] (5) (molecule 1 only shown) with the atomic
labeling scheme.

86
K. Raghuraman et al. / Journal of Organometallic Chemistry 669 (2003) 79Á86
/
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the available information on these systems is admittedly
limited. The synthetic methodology reported in this
paper can be extended to other chiral diphosphazane
monosulfides and monoselenides to prepare chalcogen
monocapped ruthenium carbonyl clusters, especially
those containing a streogenic centre at the phosphorus
or the substituent(s) attached to phosphorus. These
ruthenium clusters as well as the rhodium, palladium
and platinum complexes, (which are readily formed by
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(b) M.S. Balakrishna, S. Teipal, A.A. Pinkerton, R.G. Cavell,
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Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC nos. 133688 and 189175 for
compounds 3 and 5, respectively. Copies of this
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge CB2 1EZ,
(c) R.P.K. Babu, S.S. Krishnamurthy, M. Nethaji, Tetrahedron:
Asymmetry 6 (1995) 427;
(d) K. Raghuraman, S.S. Krishnamurthy, M. Netahji, J. Chem.
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[12] E. Simo´n-Manso, M. Valderrama, P. Gantzel, C.P. Kubiak, J.
Organomet. Chem. 651 (2002) 90.
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[13] J.A. Mccleverty, G. Wilkinson, Inorg. Synth. 28 (1990) 84.
[14] D. Drew, J.R. Doyle, Inorg. Synth. 28 (1990) 346.
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6. Note added in proof
[16] D. Cauzzi, C. Graiff, C. Massera, G. Predieri, A. Tiripicchio, in:
P. Brunstein, L.A. Oro, P.R. Raithby (Eds.), Metal Clusters in
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chloride complexes have been reported recently by
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Chemistry, vol. I, WileyÁ
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