Phenylmercury(II) derivatives of tetraorganodichalcogenoimidodiphosphorus acids. Crystal and molecular structure of [PhHg{(OPR2) (SPPh2)N}]2 (R=Me, Ph)

Article abstract of DOI:10.1016/j.jorganchem.2003.07.016

The reactions between PhHgCl or PhHgAc and M[(XPR₂) (YPR′₂)N] (M=Na, K; X, Y=O, S; R, R′=Me, Ph, OEt), in 1:1 molar ratio, have been investigated. PhHg[(XPR₂) (YPR′₂)N] derivatives were isolated as microcrystalline powders and were characterised using IR and NMR (¹H, ¹³C and ³¹P) spectroscopy and mass spectrometry. The molecular structure of PhHg[(OPR₂) (SPPh₂)N] [R=Me (1), Ph (2)] was investigated by X-ray diffraction. In the monomeric unit, PhHg[(OPR₂)(SPPh₂)N], the mercury atom forms the primary bonds with the carbon of the phenyl group and the sulfur atom of the phosphorus ligand [Hg(1)-S(1) 2.405(1) ? for 1, 2.398(2) ? for 2]. These primary bonds are significantly deviated from the expected linear arrangement [C(1)-Hg(1)-S(1) 166.4(2)° for 1, 165.0(2)° for 2]. Both compounds exhibit dimeric associations in the crystal through S, O -bridging organophosphorus ligands [Hg(1)-O(1) 2.556(4) ? for 1, 2.588(4) ? for 2], thus resulting in a distorted T-shaped arrangement of the CHgSO coordination core.. The formation of a 12-membered Hg₂O₂S₂ P₄N₂ ring with different conformation in 1 and 2, respectively, results in different additional chalcogen atoms being in the proximity of the metal atom. Weak transannular Hg?O [2.753(4) ?] are also established in 1, leading to a tricyclic ladder structure with a planar central Hg₂O₂ ring.

Full text of DOI:10.1016/j.jorganchem.2003.07.016

Journal of Organometallic Chemistry 687 (2003) 118ꢁ124
/
www.elsevier.com/locate/jorganchem
Phenylmercury(II) derivatives of
tetraorganodichalcogenoimidodiphosphorus acids. Crystal and
molecular structure of [PhHg{(OPR2)(SPPh2)N}]2 (RꢀMe, Ph)
/
Oana Bumbu a, Anca Silvestru a,*, Cristian Silvestru a, John E. Drake b,
Michael B. Hursthouse c, Mark E. Light c
a Facultatea de Chimie si Inginerie Chimica, Universitatea Babes-Bolyai, RO-3400 Cluj-Napoca, Romania
b Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ont., Canada N9B 3P4
c Department of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, UK
Received 26 May 2003; received in revised form 25 July 2003; accepted 25 July 2003
Abstract
?
The reactions between PhHgCl or PhHgAc and M[(XPR2)(YPR2)N] (Mꢀ
/
Na, K; X, Yꢀ
/
O, S; R, R?ꢀMe, Ph, OEt), in 1:1
/
?
molar ratio, have been investigated. PhHg[(XPR2)(YPR2)N] derivatives were isolated as microcrystalline powders and were
characterised using IR and NMR (1H, 13C and 31P) spectroscopy and mass spectrometry. The molecular structure of
PhHg[(OPR2)(SPPh2)N] [Rꢀ/Me (1), Ph (2)] was investigated by X-ray diffraction. In the monomeric unit,
PhHg[(OPR2)(SPPh2)N], the mercury atom forms the primary bonds with the carbon of the phenyl group and the sulfur atom
˚
˚
of the phosphorus ligand [Hg(1)ꢁ
expected linear arrangement [C(1)ꢁ
crystal through S,O-bridging organophosphorus ligands [Hg(1)ꢁ
/
S(1) 2.405(1) A for 1, 2.398(2) A for 2]. These primary bonds are significantly deviated from the
/
Hg(1)ꢁS(1) 166.4(2)8 for 1, 165.0(2)8 for 2]. Both compounds exhibit dimeric associations in the
/
˚ ˚
O(1) 2.556(4) A for 1, 2.588(4) A for 2], thus resulting in a
/
distorted T-shaped arrangement of the CHgSO coordination core.. The formation of a 12-membered Hg2O2S2P4N2 ring with
different conformation in 1 and 2, respectively, results in different additional chalcogen atoms being in the proximity of the metal
˚
atom. Weak transannular Hgꢀ ꢀ ꢀO [2.753(4) A] are also established in 1, leading to a tricyclic ladder structure with a planar central
Hg2O2 ring.
# 2003 Elsevier B.V. All rights reserved.
Keywords: Crystal structures; Organophosphorus ligands; Phenylmercury(II) derivatives
1. Introduction
Hg[(SePPh2)2N]2 [3], and organometallic derivatives,
i.e. PhHg[{OP(OPh)2}2N] [4,5], are known. The inor-
ganic species Hg[(SePPh2)2N]2 was found to exhibit a
spiro NP2Se2HgSe2P2N core with tetrahedral coordi-
nated metal center due to the expected Se,Se-chelating
nature of the ligand moieties [3]. By contrast, unusual
N,O-bridging imidodiphosphorus ligands led to dimeric
species in the crystal of PhHg[{OP(OPh)2}2N] (Fig. 1a).
The reaction of HgO with [OP(OPh)2]2NH or (OPE-
t2}[OP(OPh)2]NH resulted in ortho-mercuration of a
phenoxy group and isolation of dinuclear compounds,
The large bite and high flexibility of the tetraorgano-
dichalcogenoimidodiphosphorus anions make them ver-
satile ligands towards metallic and organometallic
centers. A variety of structures has been reported for
complexes of Main Group elements, including Group 12
metals, due to the coordination opportunities offered
both by metals and ligands [1]. Only a few mercury(II)
compounds containing imidodiphosphorus ligands, i.e.
inorganic Hg[(SPPh2)2N]2, HgCl[(SPPh2)2N] [2],
Hg2[(OPR2){OP(OPh)(OC6H4-2)}N]2 (RꢀEt [6], OPh
/
[4]) (Fig. 1b). The second covalence at the mercury atom
is achieved through a Hg-N bond which involves the
nitrogen of a neighboring mercurated imidodiphospho-
ric ligand, thus resulting in the formation of a 12-
* Corresponding author. Tel.: ꢂ
818.
E-mail address: ancas@chem.ubbcluj.ro (A. Silvestru).
/
40-64-193-833; fax: ꢂ40-64-190-
/
0022-328X/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2003.07.016

O. Bumbu et al. / Journal of Organometallic Chemistry 687 (2003) 118ꢁ
/124
119
membered Hg2C4O2P2N2 ring with almost linear Nꢁ
/
2. Results and discussion
HgꢁC fragments.
/
In the context of our interest in the coordination
chemistry of imidodiphosphorus ligands [1], we decided
to investigate the influence of the nature of the chalco-
2.1. Preparation
The title compounds were prepared according to Eq.
(1), by reacting stoichiometric amounts of either phe-
nylmercury(II) chloride or acetate and the alkali salt of
the appropriate tetraorganodichalcogenoimidodipho-
sphorus ligand:
gen atoms in organomercury(II) derivatives containing
ꢃ
?
ligands of the type [(XPR2)(YPR2)N] . We report here
on the synthesis and spectroscopic characterization of
some
PhHg[(XPR2)(YPR2)N], as well as the crystal and
molecular structure of PhHg[(OPR2)(SPPh2)N] [Rꢀ
phenylmercury(II)
compounds,
?
/
Me, Ph].
ð1Þ
All compounds were isolated as air-stable, colorless
crystalline products. They were characterized by multi-
nuclear (1H, 13C and 31P) NMR and IR spectroscopy
and mass spectrometry. The crystal and molecular
structures of PhHg[(OPMe2)(SPPh2)N] (1) and
PhHg[(OPPh2)(SPPh2)N] (2) were determined by single
crystal X-ray diffraction.
2.2. IR spectra
IR bands were assigned for nas(P2N), n(PO) and n(PS)
stretching vibrations by comparison with the free
?
(XPR2)(YPR2)NH acids and their alkali salts [7ꢁ
/9].
The presence of strong absorptions in the region 1290ꢁ
/
1200 cmꢃ1, assigned to nas(P2N) stretching vibration,
and the absence of strong absorptions characteristic for
the free acids around 2700ꢁ
/
2600 [n(NH)] and 950ꢁ900
/
cmꢃ1 [nas(P2NH)], indicates that the imidodiphosphorus
moieties are coordinated to the metal center in the
deprotonated form.
2.3. NMR spectra
1
The H- and 13C-NMR spectra of compounds 1ꢁ
/
4
show the expected resonances and suggest that the
organic groups attached to the same phosphorus atom
are equivalent on the NMR time scale at room
temperature. In all cases the lower field resonance in
1
the H-NMR spectra (d ca. 8 ppm) is due to the ortho
protons of the Pꢁ
pattern due to phosphorusꢁ
carbon couplings were observed. Satellites due to
199Hgꢁ13C coupling surround the 13C resonances as-
signed to the ortho and meta carbons of the phenyl
group on the metal atom.
/
C6H5 group. The expected splitting
/
proton and phosphorusꢁ
/
Fig. 1. (a) Dimeric association in the crystal of PhHg[{OP(OPh)2}2N]
[5] (for clarity, only carbons bound to oxygen atoms in the ligand
moiety are shown); (b) the structure of dinuclear complex Hg2[(OPE-
t2){OP(OPh)(OC6H4-2)}N]2 [4].
/

120
O. Bumbu et al. / Journal of Organometallic Chemistry 687 (2003) 118ꢁ124
/
The 31P-NMR spectra of compounds 1ꢁ
4 exhibit two
/
resonances, as is expected in the presence of the non-
equivalent phosphorus atoms in a ligand moiety. Only
in the case of 3 is a resolved doublet pattern due to
phosphorusꢁphosphorus coupling observed for both
/
31P signals. The magnitude of the chemical shifts
suggests that both calcogen atoms of the ligand unit
are involved in coordination to the metal center, e.g. d
21.1 (PO), 28.8 (PS) for 2, compared to 28.9 (PO), 41.8
(PS) for Meꢁ
(PS) for OꢀPPh2ꢁ
[10].
/
Oꢁ
/
PPh2ꢀ
/
Nꢁ
/
PPh2ꢀ
/
S and 13.3 (PO), 26.7
/
/
NꢀPPh2ꢁ
/
/
SꢁMe esters, respectively
/
2.4. Mass spectra
The mass spectra of compounds 1ꢁ
/
3 exhibit highly
abundant [Mꢂꢂ
/H] fragments, which represent the
Fig. 3. ORTEP plot of the discrete dimer in the crystal of 2. The atoms
are drawn with 20% probability ellipsoids. Hydrogen atoms are
omitted for clarity.
molecular ion for compounds 2 and 3 in the FAB-MS.
In addition, the DCI-MS spectrum of 1 and the FAB-
MS spectra of 2 and 3 show higher m/z ions corre-
respectively. Selected interatomic distances and angles
are listed in Table 1.
There are some common structural features for both
compounds:
sponding to [M2ꢂꢂ
/
H] (1) and [M2ꢂ] (2) as well as
2H] (3). This supports the dimeric associa-
[M2ꢂ ꢃ
tion established by the single-crystal X-ray diffraction
studies for 1 and 2.
/
Phꢂ
/
i) in the monomeric unit, PhHg[(OPR2)(SPPh2)N], the
mercury atom forms the primary bonds with the
2.5. Crystal and molecular structure of
PhHg[(OPMe2)(SPPh2)N] (1) and
PhHg[(OPPh2)(SPPh2)N] (2)
Table 1
a
˚
Selected interatomic distance (A) and bond angles (8) in 1 and 2
Crystals suitable for single-crystal X-ray diffraction
analysis were obtained for compounds 1 and 2 from a
mixture of chloroform and hexane (1/4, v/v). In both
cases the crystals consist of discrete dimeric units
separated by normal van der Waals distances. The
ORTEP diagrams for compounds 1 and 2 with the
atom numbering scheme are depicted in Figs. 2 and 3,
1
2
Bond lengths
Hg(1)ꢁ
Hg(1)ꢁ
Hg(1)ꢁ
/
C(1)
S(1)
O(1)
2.076(6)
2.405(1)
2.556(4)
2.048(2)
1.587(4)
1.610(4)
1.509(4)
2.753(4)
3.872(1)
3.471(4)
2.058(7)
2.398(2)
2.588(4)
2.060(2)
1.574(5)
1.602(6)
1.494(5)
3.313(2)
4.197(1)
3.899(5)
/
/
P(1)ꢁ
P(1)ꢁ
P(2)ꢁ
P(2)ꢁ
/
S(1?)
N(1)
N(1)
O(1)
/
/
/
Hg(1)ꢀ ꢀ ꢀX(1?) b
Hg(1)ꢀ ꢀ ꢀHg(1?)
O(1)ꢀ ꢀ ꢀS(1?)
Bond angles
C(1)ꢁ
C(1)ꢁ
S(1)ꢁHg(1)ꢁ
Hg(1?)ꢁS(1?)ꢁ
S(1?)ꢁP(1)ꢁ
P(1)ꢁN(1)ꢁ
O(1)ꢁP(2)ꢁ
Hg(1)ꢁO(1)ꢁ
X(1?)ꢀ ꢀ ꢀHg(1)ꢁ
X(1?)ꢀ ꢀ ꢀHg(1)ꢁ
X(1?)ꢀ ꢀ ꢀHg(1)ꢁ
Hg(1)ꢀ ꢀ ꢀX(1?)ꢁ
/
Hg(1)ꢁ
/
S(1)
166.4(2)
104.9(2)
85.91(8)
97.18(6)
118.6(2)
131.1(3)
116.9(2)
136.7(2)
104.3(2)
84.30(8)
86.4(1)
165.0(2)
99.2(2)
94.5(1)
/
Hg(1)ꢁ
/
O(1)
/
/O(1)
/
/P(1)
92.67(8)
115.8(2)
134.7(4)
119.6(3)
133.7(3)
101.3(2)
86.77(5)
94.5(1)
/
/
N(1)
P(2)
/
/
/
/N(1)
/
/
P(2)
/
C(1) b
S(1) b
/
/
O(1) b
Hg(1?) b
/
93.6(1)
93.2(1)
a
Symmetry equivalent position given by a ‘prime’ for 1 (ꢃ
1, ꢃzꢂ1) and for 2 (ꢃx, ꢃy, ꢃz), respectively.
X(1?)ꢀO(1?) for 1 and S(1?) for 2.
/
xꢂ
/
1, ꢃ
/
Fig. 2. ORTEP plot of the discrete dimer in the crystal of 1. The atoms
are drawn with 25% probability ellipsoids. Hydrogen atoms are
omitted for clarity.
yꢂ
/
/
/
/
/
/
b
/

O. Bumbu et al. / Journal of Organometallic Chemistry 687 (2003) 118ꢁ
/124
121
˚
C(1) 2.076(6) A
for 1, 2.058(7) A for 2] and the sulfur atom of the
carbon of the phenyl group [Hg(1)ꢁ
/
˚
˚
phosphorus ligand [Hg(1)ꢁS(1) 2.405(1) A for 1,
/
˚
2.398(2) A for 2]. These primary bonds are sig-
nificantly deviated from the expected linear arrange-
ment [C(1)ꢁ
for 2]. Their magnitude is comparable with those
observed, for example, in [PhHg{S(S)PEt2}]n [Hgꢁ
/
Hg(1)ꢁS(1) 166.4(2)8 for 1, 165.0(2)8
/
/
˚
˚
C 2.062(11) A, HgꢁS 2.375(4) A] [11].
/
ii) the monomeric units are associated into discrete
dimers, [PhHg{(OPR2)(SPPh2)N}]2, through S,O-
bridging monothioimidodiphosphinato ligands. The
mercuryꢁ/oxygen interactions within the twelve-
membered Hg2O2S2P4N2 ring thus formed [Hg(1)ꢁ
/
˚
˚
O(1) 2.556(4) A for 1, 2.588(4) A for 2] are
considerably shorter than the sum of the van der
Waals radii for the corresponding atoms
˚
[SvdW(Hg,O) 3.0 A] [12]. These interatomic interac-
tions are stronger than the intra- [Hgꢀ ꢀ ꢀO 2.897(4)
˚
˚
A] or inter-dimer [Hgꢀ ꢀ ꢀO 2.831(3) A] interactions
observed in the ribbon-like structure of
[MeHg{S(O)PPh2}]n [13]. They are also shorter
than the HgꢁO bond in the dimeric association
/
based on N,O-bridging ligand which was described
for the related derivative PhHg[{OP(OPh)2}2N]
˚
O 2.684(5) A] [5].
[Hgꢁ
/
iii) the CHgSO cores exhibit a distorted T-shaped
coordination geometry; the sum of the bond angles
around the mercury atom being closed to 3608, i.e.
357.28 for 1, and 358.78 for 2.
iv) the bond lengths within the SPNPO skeleton are
consistent with S-covalent bonded bridging ligands,
i.e. single phosphorusꢁ
/
sulfur bonds [P(1)ꢁ
/
S(1?)
2.048(2) A for 1, 2.060(2) A for 2] and considerable
double bond character for the phosphorusꢁoxygen
˚
˚
/
˚
˚
bonds [P(2)ꢁ
(cf. [2ꢁ(Me2NCH2)C6H4]Teꢁ
[14]: PꢁS 2.057(1), PꢀS 1.945(1) A; Ph2P(ꢀ
[15]: PꢁO 1.526(6), Pꢀ
the lengths of the phosphorusꢁ
(Table 1) are consistent with some delocalization
within the HgꢁSꢁPꢀNꢁPꢀO0Hg fragment (cf. [2-
(Me2NCH2)C6H4]TeꢁSꢁPPh2ꢀNꢁPPh2ꢀS [14]: Pꢁ
N 1.612(3), PꢀN 1.557(3) A).
/
O(1) 1.509(4) A for 1, 1.494(5) A for 2]
SꢁPPh2ꢀNꢁPPh2ꢀ
O)OH
O 1.486(6) A). Accordingly,
nitrogen bonds
Fig. 4. Conformation of the 12-membered Hg2O2S2P4N2 inorganic
rings in the dimeric associations of compounds 1 and 2.
/
/
/
/
/
/S
˚
/
/
/
˚
/
/
of the sum of the van der Waals radii [SvdW(Hg,O) 3.0
/
˚
˚
A, SvdW(Hg,S) 3.3 A] [12]. If these weak interatomic
contacts are considered, the overall tricyclic system
features a ladder structure with SPNP and OPNP
fragments for 1 and 2, respectively, placed on opposite
/
/
/
/
/
/
/
/
/
/
/
/
˚
/
sides of the central planar Hg2X2 core (XꢀO, S). The
/
˚
magnitude of the Hg(1)ꢀ ꢀ ꢀHg(1?) distances [3.872(1) A
There are also significant differences between the
dimeric units found in the crystals of 1 and 2, mainly
related to the conformation of the twelve-membered
inorganic rings (Fig. 4). The bond angles within the
Hg2O2S2P4N2 rings of the dimeric associations (Table 1)
are of the same magnitude, but the rings are twisted to
bring the second oxygen atom in 1 or the second sulfur
atom in 2 into the proximity of the mercury atom. The
transannular metal-chalcogen distances indicate signifi-
˚
for 1 and 4.197(1) A for 2] within the Hg2X2 cores is
consistent with the absence of any interactions between
the metal atoms. The external cyclic HgOSP2N systems
exhibit distorted chair conformation in 1, with Hg and
N atoms in the apices, and distorted boat conformation
in 2, with O and P atoms in the apices [the dihedral angle
between
the
best
O(1)Hg(1)S(1a)P(1)
and
O(1)P(2)N(1)P(1) planes is 142.48]. The orientation of
the phenyl groups attached to mercury atoms is also
different: they are trans with respect to the Hg2O2
˚
cant secondary bonding in 1 [Hg(1)ꢀ ꢀ ꢀO(1?) 2.753(4) A],
˚
while in 2 [Hg(1)ꢀ ꢀ ꢀS(1?) 3.313(2) A] they are at the limit

122
O. Bumbu et al. / Journal of Organometallic Chemistry 687 (2003) 118ꢁ124
/
system in 1 (Fig. 4a), while the ipso carbons of the
aromatic groups are basically coplanar with the Hg2S2
system in 2 (Fig. 4b).
was separated by filtration, washed with n-hexane and
dried in vacuum. Details of the preparations and melting
points are given in Table 2. Microanalysis (C, H, N) and
NMR spectra are consistent with the given composition
of the isolated products.
3. Conclusions
4.2.1. PhHg[(OPMe2)(SPPh2)N] (1)
Anal. Found: C, 40.7; H, 3.5; N, 2.5. Calc. for
C20H21HgNOP2S: C, 41.0; H, 3.6; N, 2.4%. IR
?
New PhHg[(XPR2)(YPR2)N] (X, Yꢀ
/
O, S; R, R?ꢀ
/
Me, Ph, OEt) derivatives were prepared and character-
ized using IR and NMR (1H, 13C and 31P) spectroscopy
and mass spectrometry. Evidence for the presence of
dimeric associations was obtained from MS data. The
(cmꢃ1): 1210vs [nas(P2N)], 1107vs [n(PO)], 560s
2
[n(PS)]. 1H-NMR: d 1.55dd (6H, Pꢁ
/
CH3, JPH 13.9,
4JPH 1.6 Hz), 7.22tt (1H, Hgꢁ
1.5 Hz), 7.32dd (2H, Hgꢁ
7.45m (8H, PꢁC6H5-metaꢂ
7.94ddd (4H, PꢁC6H5-ortho, JPH 14.0, JHH 7.9, JHH
1.6 Hz). 13C-NMR: d 21.31dd (Pꢁ
4.6 Hz), 128.41s (HgꢁC6H5-para), 128.61d (Pꢁ
/
C6H5-para, 3JHH 7.5, 4JHH
3
molecular structure of PhHg[(OPR2)(SPPh2)N] [Rꢀ
/Me
/
C6H5-meta, JHH 7.5 Hz),
(1), Ph (2)] was investigated by X-ray diffraction. Both
compounds exhibit dimeric associations in the crystal
through S,O-bridging organophosphorus ligands, re-
sulting in 12-membered inorganic rings and distorted T-
shaped CHgSO cores with the sulfur atom trans to the
aromatic ipso carbon. The Hg2O2S2P4N2 rings are
twisted in different ways to bring an additional oxygen
and sulfur atoms in 1 and 2, respectively, into the
proximity of the metal, thus leading to overall tricyclic
ladder structures with central Hg2O2 and Hg2S2 planar
cores.
/
/
para, HgꢁC6H5-ortho),
/
3
3
4
/
1
3
/
CH3, JPC 92.7, JPC
/
/
C6H5-
3
3
meta, JPC 13.7 Hz), 128.73s (Hgꢁ
/
C6H5-meta, JHgC
2
190.1 Hz), 130.85d (PꢁC6H5-ortho, JPC 11.5 Hz),
/
4
131.67d (Pꢁ
/
C6H5-para, JPC 2.3 Hz), 136.94s (Hgꢁ
/
2
C6H5-ortho, JHgC 116.8 Hz), 137.84dd (Pꢁ
/
C6H5-ipso,
C6H5-ipso). 31P-
1JPC 111.1, JPC 4.6 Hz), 156.82s (Hgꢁ
/
3
NMR: d 25.8s, br (Me2PO), 36.8s, br (Ph2PS). MS
[DCIpos, NH3, 8 mA sꢃ1, m/z (%)]: 1173 (7) [M2ꢂꢂ
H],
864 (5) [M2ꢂ ꢃL], 819 (28) [M2ꢂ ꢁ
PhHgꢂH], 588 (76)
[MꢂꢂH], 310 (100) [PhMeHgꢂꢂ
NH3], 296 (78)
[PhHgꢂꢂ
NH3].
/
/
/
/
/
/
4. Experimental
/
4.1. Materials and procedures
4.2.2. PhHg[(OPPh2)(SPPh2)N] (2)
Anal. Found: C, 50.4; H, 3.8; N, 1.8. Calc. for
C30H25HgNOP2S: C, 50.7; H, 3.6; N, 2.0%. IR
(cmꢃ1): 1272vs [nas(P2N)], 1146vs [n(PO)], 555vs
The starting materials were prepared according to
literature
K[(OPPh2)(SPPh2)N] [7], K[{OP(OEt2)}(SPPh2)N], [9]
K[{OP(OEt2)}(OPPh2)N] [9], PhHgCl and
methods:
Na[(OPMe2)(SPPh2)N],
[8]
[n(PS)]. 1H-NMR:
metaꢂpara, HgꢁC6H5-metaꢂ
C6H5-ortho, JHH 6.9 Hz), 7.92m (8H, Pꢁ
d
7.48ꢁ
/
7.22m (15H, Pꢁ
para), 7.52d (2H, Hgꢁ
C6H5-ortho).
/
C6H5-
/
/
/
/
3
PhHgO(O)CCH3 [16]. Solvents were dried on potassium
(toluene) and sodium (n-hexane) and freshly distilled
prior to use. Infrared spectra were recorded in the range
/
13Cꢁ
128.38s (Hgꢁ
13.7 Hz), 128.65s (Hgꢁ
130.32d (Pꢁ
C6H5-para, 4JPC 2.3 Hz), 130.94d (Pꢁ
ortho, 2JPC 11.4 Hz), 131.22d (PꢁC6H5-ortho, 2JPC 10.3
Hz), 131.60d (Pꢁ
C6H5-para, 4JPC 3.4 Hz), 137.04s (Hgꢁ
C6H5-ortho, JHgC 116.8 Hz), 137.47dd [P(S)ꢁC6H5-
C6H5-
C6H5-ipso).
/
NMR: d 128.02d (Pꢁ/C6H5-meta, JPC 12.6 Hz),
3
3
/
C6H5-para), 128.52d (Pꢁ
/
C6H5-meta, JPC
3
4000ꢁ
/
250 cmꢃ1 as KBr pellets on a Jasco FT/IR-615
/C6H5-meta, JHgC 190.2 Hz),
instrument. The H-, 13C- and 31P-NMR spectra were
recorded on a VARIAN GEMINI 300S instrument
operating at 299.5, 75.4 and 121.4 MHz, respectively, at
room temperature, in CDCl3. The chemical shifts are
reported in ppm relative to TMS and H3PO4 85%,
respectively. Mass spectra were recorded on a VG
Autospec.3. spectrometer.
/
/
C6H5-
1
/
/
/
2
/
1
3
ipso, JPC 112.2, JPC 4.6 Hz], 138.58dd [P(O)ꢁ
/
1
3
ipso, JPC 132.2, JPC 4.6 Hz], 157.07s (Hgꢁ
/
1
31P-NMR: d 21.1s (Ph2PO, JPC 128.7 Hz), 28.8s
1
(Ph2PS, JPC 117.0 Hz). MS [FABpos, m/z (%)]: 1420
4.2. Preparation of the title compounds,
?
PhHg[(XPR2)(YPR2)N] (Table 2)
(3) [M2ꢂ], 988 (8) [M2ꢂ ꢃ
/
L], 712 (100) [Mꢂꢂ
H], 634
/
(45) [Mꢂ ꢃ
/Ph].
Mixtures of either PhHgCl or PhHgOCOCH3 and
?
the appropriate alkali salt, M[(XPR2)(YPR2)N] (1:1
4.2.3. PhHg[{OP(OEt)2}(SPPh2)N] (3)
Anal. Found: C, 40.7; H, 3.6; N, 2.1. Calc. for
C22H25HgNO3P2S: C, 40.9; H, 3.9; N, 2.2%. IR
(cmꢃ1): 1290s, 1260s [nas(P2N)], 1190vs, 1102s [n(PO)],
molar ratio) in 40 ml toluene were refluxed for 18 h
and then filtered to remove the resulting alkali metal
salt. The filtrate was evaporated under reduced pressure
and an oily product was obtained. After stirring for 30
min. with n-hexane, a white solid was deposited. This
1037vs [n(POC)], 565s [n(PS)]. 1H-NMR: d 1.29t (6H, P-
3
OCH2CH3, JHH 6.9 Hz), 4.07dq (4H, Pꢁ
/
OCH2CH3,
C6H5-para, 3JHH
3JPH 7.1, 3JHH 7.1 Hz), 7.23t (1H, Hgꢁ
/

O. Bumbu et al. / Journal of Organometallic Chemistry 687 (2003) 118ꢁ
/124
123
Table 2
Preparation data and m.p. for PhHg[(XPR2)(YPR2)N] derivatives
?
Starting materials
Product [yield: g (%)]
m.p. (8C)
ꢃ1
PhHgL (g mmolꢃ1
)
)
?
M[(XPR2)(YPR2)N] (g mmol
PhHgCl
0.313/1.00
Na[(OPMe2)(SPPh2)N]
0.331/1.00
PhHg[(OPMe2)(SPPh2)N] (1)
0.378 (65)
138
PhHgOCOCH3
0.337/1.00
K[(OPPh2)(SPPh2)N]
0.471/1.00
PhHg[(OPPh2)(SPPh2)N] (2)
0.506 (71)
116ꢁ
/
118
92 (dec.)
132 (dec.)
PhHgOCOCH3
0.337/1.00
K[{OP(OEt2)}(SPPh2) N]
0.407/1.00
PhHg[{OP(OEt2)}(SPPh2) N] (3)
0.497 (77)
PhHgOCOCH3
0.337/1.00
K[{OP(OEt2)}(OPPh2) N]
0.391/1.00
PhHg[{OP(OEt2)}(OPPh2) N] (4)
0.327 (52)
130ꢁ
/
3
7.2 Hz), 7.32dd (2H, Hgꢁ
7.46m (8H, PꢁC6H5-metaꢂ
8.00ddd (4H, PꢁC6H5-ortho, JPH 14.3, JHH 7.8, JHH
1.5 Hz). 13C-NMR: d 16.38d (Pꢁ
/
C6H5-meta, JHH 7.2 Hz),
experimental parameters. An absorption correction
was applied [18]. The structures were solved by direct
methods [19] and the structure was refined using the
WINGX version [20] of SHELX-97 [21]. All of the non-
hydrogen atoms were treated anisotropically. The phen-
yl ring attached to Hg displays considerable disorder
and can be modelled but with no significant influence on
/
/
para, HgꢁC6H5-ortho),
/
3
3
4
/
3
/
OCH2CH3, JPC 8.0
2
Hz), 61.86d (P-OCH2CH3, JPC 5.7 Hz), 128.52s (Hgꢁ
/
3
C6H5-meta, JPC 13.7 Hz),
C6H5-para), 128.53d (Pꢁ
/
3
128.70s (Hgꢁ
(Pꢁ
4JPC 3.5 Hz), 136.88s (Hgꢁ
/
C6H5-meta, JHgC 190.1 Hz), 130.99d
2
/
C6H5-ortho, JPC 11.5 Hz), 131.79d (Pꢁ
/
C6H5-para,
C6H5-ortho, 2JHgC 113.4 Hz),
/
1
3
Table 3
X-ray crystal data and structure refinement for 1 and 2
137.00dd (Pꢁ
/
C6H5-ipso, JPC 113.4, JPC 6.9 Hz),
C6H5-ipso). 31P-NMR:
4.49d
[(EtO)2PO, JPP 21.4 Hz], 30.4d (Ph2PS, JPP 21.4
Hz). MS [FABpos, m/z (%)]: 1217 (15) [M2ꢂ ꢃ
Phꢂ
2H], 648 (100) [MꢂꢂH], 570 (17) [Mꢂ ꢃ
Ph].
156.74s (Hgꢁ
/
d
2
2
1
2
/
/
Empirical formula
Formula weight
Temperature (K)
C40H42O2N2P4S2Hg2 C60H50O2N2P4S2Hg2
1171.94
299(2)
/
/
1420.20
299(2)
˚
Wavelength (A)
0.71073
Monoclinic
P21/n
0.71073
Orthorhombic
Pbca
4.2.4. PhHg[{OP(OEt)2}(OPPh2)N] (4)
Crystal system
Space group
Unit cell dimensions
Anal. Found: C, 41.7; H, 3.9; N, 2.1. Calc. for
C22H25HgNO4P2: C, 41.9; H, 4.0; N, 2.2%. IR (cmꢃ1):
1260s [nas(P2N)], 1183vs, 1120m [n(PO)], 1042vs
˚
a (A)
9.057(2)
11.905(2)
19.799(4)
97.93(3))
2114.4(7)
2
23.176(5)
9.641(2)
24.947(5)
1
3
˚
b (A)
[n(POC)]. H-NMR: d 1.03t (6H, Pꢁ
/
OCH2CH3, JHH
˚
c (A)
3
3
7.0 Hz), 3.82dq (4H, Pꢁ
Hz), 7.28m (11H, PꢁC6H5-metaꢂ
7.88ddd (4H, PꢁC6H5-ortho, JPH 12.3, JHH 7.5, JHH
1.4 Hz). 13C-NMR: d 16.04d (Pꢁ
/OCH2CH3, JPH 7.0, JHH 7.0
b (8)
/
/
para, HgꢁC6H5),
/
3
V (A )
˚
5574(2)
4
3
3
4
/
Z
3
Dcalc (g cmꢃ3
Absorption coeffi-
)
1.841
7.538
1.692
5.736
/
OCH2CH3, JPC 6.8
OCH2CH3, JPC 5.7 Hz), 127.98s (Pꢁ
C6H5-meta, JPC 12.6 Hz), 128.97s (HgꢁC6H5-para),
129.20s (HgꢁC6H5-meta), 130.85s (PꢁC6H5-para),
131.68d (PꢁC6H5-ortho, JPC 11.1 Hz), 136.62s (Hgꢁ
C6H5-ortho), 136.57d (Pꢁ
2
Hz), 62.21d (Pꢁ
/
/
cient (mmꢃ1
)
3
/
F(000)
1128
2768
/
/
Crystal size (mm3)
u Range for data
collection (8)
0.20ꢄ
/
0.15ꢄ
/
0.10
0.40ꢄ
/
0.15ꢄ0.15
/
2
/
/
2.92ꢁ30.33
/
2.40ꢁ27.48
/
1
/C6H5-ipso, JPC 129.4 Hz),
146.36s (Hgꢁ
C6H5-ipso). 31P-NMR: d 5.0d [(EtO)2PO,
/
Reflections collected 14747
Independent reflec-
tions
28099
6360 [Rint
2JPP 11.7 Hz], 20.3s,br (Ph2PO).
5199 [Rint
ꢀ
/
0.0513]
ꢀ/0.0811]
Data/restraints/para- 5199/0/237
meters
6360/0/325
1.005
4.3. X-ray structure determination
Goodness-of-fit on
F2
1.018
Final R indices [F2ꢀ
/
R1ꢀ
0.0866
R1ꢀ0.0714, wR2ꢀ
0.0978
1.364 and ꢃ
/0.0416, wR2ꢀ
/
R1ꢀ
0.1003
R1ꢀ0.1089, wR2ꢀ
0.1197
0.902 and ꢃ
/
0.0480, wR2ꢀ
/
Block crystals of 1 and 2 were mounted on glass
fibres. Data were collected on an EnrafꢁNonius Kap-
paCCD area detector diffractometer, with 8 and v
scans chosen to give a complete asymmetric unit. Cell
refinement [17] gave cell constants corresponding to a
monoclinic (for 1) and orthorhombic (for 2) cells whose
dimensions are given in Table 3 along with other
2s(F2)]
/
R indices (all data)
/
/
/
/
Largest difference
peak and hole (e
/1.863
/0.984
ꢃ3
˚
A
)

124
O. Bumbu et al. / Journal of Organometallic Chemistry 687 (2003) 118ꢁ124
/
the overall refinement. Hydrogen atoms were included
in idealized positions with isotropic thermal parameters
set at 1.2 times that of the carbon atom to which they
were attached. The final cycle of full-matrix least-
squares refinement was based on 5199 for 1 and 6360
for 2 observed reflections [3694 for 1 and 3571 for 2 for
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This work was supported by the National University
Research Council of Romania (CNCSIS). M.B.H.
thanks the UK Engineering and Physical Sciences
Council for support of the X-ray facilities at South-
ampton. J.E.D. thanks the Natural Sciences and En-
gineering Research Council of Canada for financial
support.
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1997.