Group 11 metal complexes of the mesocyclic thioether aminophosphonites [-OC10H6(μ-S)C10H6O-]PNC 4H8E (E = O, NMe)

Article abstract of DOI:10.1002/ejic.200600913

Group 11 metal complexes of the mesocyclic thioether aminophosphonites [-OC₁₀H₆(μ-S)C₁₀H₆O-]PNC ₄H₈E {2a: E = O; 2b: E = NMe; IUPAC names: 4-(dinaphtho[2,1-d:1′,2′-g][1,3,6,2]dioxathiaphosphocin-4-yl) morpholine (2a), 1-(dinaphtho[2,1-d:1′,2′-g][1,3,6,2] dioxathiaphosphocin-4-yl)-4-methylpiperazine (2b)} are reported. Thioether aminophosphonites 2a and 2b react with CuX (X = Cl, Br, and I) in a 1:1 molar ratio to give the tricoordinate, dimeric complexes [{[{-OC₁₀H ₆(μ-S)C₁₀H₆O-}PNC₄H ₈E-κP]Cu(μ-X)}₂] (4a: E = O, X = Cl; 4b: E = NMe, X = Cl; 5a: E = O, X = Br; 5b: E = NMe, X = Br; 6a: E = O, X = I; 6b: E = NMe, X = I), whereas with 2:1 molar ratios monomeric complexes of the type [{[-OC₁₀H₆(μ-S)C₁₀H₆O-]PNC ₄H₈O-κP}₂CUX] (7a: E = O, X = Cl; 7b: E = NMe, X = Cl; 8a: E = O, X = Br; 8b: E = NMe, X = Br; 9a: E = O, X = I; 9b: E = NMe, X = I) are obtained in excellent yield. The P,S-chelated cationic complexes [{[-OC₁₀H₆(μ-S)C₁₀H₆O-]PNC ₄H₈E-κP,κS}₂CU]BF₄ (10a: E = O; 10b: E = NMe) are obtained when 2a and 2b are treated with half an equivalent of [(MeCN)₄Cu]BF₄. Similarly, the silver complexes [{[{-OC₁₀H₆(μ-S)C₁₀H ₆O-}PNC₄H₈E-κP,κS]-AgCF ₃SO₃}₂] (11a: E = O: 11b: E = NMe) and [{[-OC₁₀H₆(μ-S)C₁₀H₆O-]PNC ₄H₈E-κP,κS}Ag(PPh₃)]CF ₃SO₃ (12a: E = O; 12b: E = NMe) are synthesized by the treatment of thioether aminophosphonites 2a and 2b with AgOTf and [Ag(PPh ₃)][OTf], respectively. Reactions of 2a and 2b with [AuCl(SMe ₂)] produce the simple monomeric gold(I) complexes [{[-OC ₁₀H₆(μ-S)C₁₀H₆O-]PNC ₄H₈E-κP}AuCl] (13a: E = O; 13b: E = NMe). The iodo derivatives [{[-OC₁₀H₆(μ-S)-C₁₀H ₆O-]PNC₄H₈E-κP}AuI] (14a: E = O; 14b: E = NMe) are obtained by the halide-exchange reaction of 13a and 13b with CuI at room temperature. The structures of complexes 5a, 7a, 8a, 13a, 13b, and 14a are confirmed by single-crystal X-ray diffraction studies. In all of these complexes, the sulfur atom in the mesocyclic ring shows coordinative interaction towards the phosphorus atom, and in 5a, 7a, 8a, and 14a towards the metal center as well. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Full text of DOI:10.1002/ejic.200600913

FULL PAPER
DOI: 10.1002/ejic.200600913
Group 11 Metal Complexes of the Mesocyclic Thioether Aminophosphonites
[-OC10H6(µ-S)C10H6O-]PNC4H8E (E = O, NMe)
Benudhar Punji,[a] Joel T. Mague,[b] and Maravanji S. Balakrishna*[a]
Keywords: Thioether-aminophosphonites / P,S ligands / Copper / Gold
Group 11 metal complexes of the mesocyclic thioether ami-
nophosphonites [-OC10H6(µ-S)C10H6O-]PNC4H8E {2a: E = O;
silver complexes [{[{-OC10H6(µ-S)C10H6O-}PNC4H8E-κP,κS]-
AgCF3SO3}2] (11a: E = O: 11b: E = NMe) and [{[-OC10H6(µ-
S)C10H6O-]PNC4H8E-κP,κS}Ag(PPh3)]CF3SO3 (12a: E = O;
12b: E = NMe) are synthesized by the treatment of thioether
aminophosphonites 2a and 2b with AgOTf and
[Ag(PPh3)][OTf], respectively. Reactions of 2a and 2b with
[AuCl(SMe2)] produce the simple monomeric gold(I) com-
plexes [{[-OC10H6(µ-S)C10H6O-]PNC4H8E-κP}AuCl] (13a: E =
O; 13b: E = NMe). The iodo derivatives [{[-OC10H6(µ-S)-
2b:
E = NMe; IUPAC names: 4-(dinaphtho[2,1-d:1Ј,2Ј-
g][1,3,6,2]dioxathiaphosphocin-4-yl)morpholine (2a), 1-(di-
naphtho[2,1-d:1Ј,2Ј-g][1,3,6,2]dioxathiaphosphocin-4-yl)-
4-methylpiperazine (2b)} are reported. Thioether aminophos-
phonites 2a and 2b react with CuX (X = Cl, Br, and I) in a
1:1 molar ratio to give the tricoordinate, dimeric complexes
[{[{-OC10H6(µ-S)C10H6O-}PNC4H8E-κP]Cu(µ-X)}2] (4a: E = O,
X = Cl; 4b: E = NMe, X = Cl; 5a: E = O, X = Br; 5b: E = NMe,
X = Br; 6a: E = O, X = I; 6b: E = NMe, X = I), whereas with
2:1 molar ratios monomeric complexes of the type
[{[-OC10H6(µ-S)C10H6O-]PNC4H8O-κP}2CuX] (7a: E = O, X =
Cl; 7b: E = NMe, X = Cl; 8a: E = O, X = Br; 8b: E = NMe, X
= Br; 9a: E = O, X = I; 9b: E = NMe, X = I) are obtained in
excellent yield. The P,S-chelated cationic complexes
[{[-OC10H6(µ-S)C10H6O-]PNC4H8E-κP,κS}2Cu]BF4 (10a: E =
O; 10b: E = NMe) are obtained when 2a and 2b are treated
with half an equivalent of [(MeCN)4Cu]BF4. Similarly, the
C10H6O-]PNC4H8E-κP}AuI] (14a: E = O; 14b: E = NMe) are
obtained by the halide-exchange reaction of 13a and 13b
with CuI at room temperature. The structures of complexes
5a, 7a, 8a, 13a, 13b, and 14a are confirmed by single-crystal
X-ray diffraction studies. In all of these complexes, the sulfur
atom in the mesocyclic ring shows coordinative interaction
towards the phosphorus atom, and in 5a, 7a, 8a, and 14a
towards the metal center as well.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2007)
based chemistry of the complexes. Although, the coordina-
tion chemistry of P,S ligands with various transition metal
derivatives has been well studied and some complexes have
proved to be active catalysts,[5] P,S ligand chemistry with
the group 11 metals is limited. Of the few complexes of
mixed P,S donor ligands with group 11 metal derivatives
that are known, some show excellent catalytic activity and
offer interesting structural features (only P or both P and S
coordination), and some bimetallic complexes show metall-
ophilic interactions that can make them ideal candidates for
luminescence studies.[6]
We recently reported the synthesis of the mesocyclic
mixed P,S ligands 2a and 2b, which exhibit an interesting
coordination behavior towards palladium and platinum de-
rivatives that results in cationic, anionic (3a, 3b), and neu-
tral complexes (Scheme 1).[7] In all compounds, the sulfur
atom present as part of an eight-membered thioether ami-
nophosphonite ring system shows a coordinative interac-
tion with phosphorus, which creates a pseudo trigonal bipy-
ramidal (TBP) geometry at the phosphorus center. All the
palladium complexes synthesized are promising catalysts
for Suzuki cross-coupling reactions, with the anionic com-
plexes 3a and 3b being particularly active (TONs of up to
92000). Since group 11 metal complexes of P,S ligands are
Introduction
In recent years, complexes of mixed-donor ligands have
been found to be more advantageous than those of ligands
having only one type of donor atom because of their cata-
lytic potential in various organic transformations.[1] In prin-
ciple, those ligands containing donor atoms with different
binding abilities are ideally suited to provide temporary co-
ordinative saturation to the metal center via chelation until
it is required to furnish an active site at the metal center
prior to oxidative addition, an important step in homogen-
eous catalysis. Among various mixed-donor ligands of the
type P,O,[2] P,N,[3] and P,S,[4] ligands combining phosphorus
and sulfur centers are especially interesting. Both phospho-
rus and sulfur are excellent donor atoms for a wide range
of metals while the low ionization energy of sulfur and the
existence of several lone pairs of electrons (three in the case
of a thiolate anion) offer the possibility of a rich sulfur-
[a] Department of Chemistry, Indian Institute of Technology
Bombay,
Powai, Mumbai 400076, India
Fax: +91-22-2576-7152, -2572-3480
E-mail: krishna@chem.iitb.ac.in
[b] Tulane University,
New Orleans, Lousiana 70118, USA
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Eur. J. Inorg. Chem. 2007, 720–731

Group 11 Complexes of Thioether Aminophosphonites
FULL PAPER
Scheme 1.
few in number, we sought to examine the reactivity of these as shown in Scheme 2. Both the chloro derivatives (4a and
thioether aminophosphonites with the group 11 metals. As 4b) and iodo derivative 6b precipitated from the reaction
part of our interest in organometallic chemistry[8] and cata- mixture as white insoluble solids, whereas the remaining
lytic investigations,[7,9] we report here on the reactivity of complexes (5a, 5b, and 6a) crystallize from the mother
the mesocyclic thioether aminophosphonites 2a and 2b with liquor either at –25 °C or at room temperature. Most of the
group 11 metal centers as well as halide-exchange reactions complexes (except for 4a and 6b) are soluble only in
of gold(I) complexes. X-ray structures of copper(I) (5a, 7a, DMSO, which allows us to carry out spectroscopic studies.
8a) and gold(I) (13a, 13b, 14a) complexes are also de- The 31P NMR spectra of complexes 4b, 5a, 5b, and 6a show
scribed.
single resonances at δ = 114.4, 113.3, 110.5, and 110.4 ppm,
respectively. In the H NMR spectra of these complexes,
1
two broad singlets are observed in the region δ = 2.49–
3.71 ppm for the CH2 protons of the morpholine and piper-
azine moieties. The mass spectrum of complex 5a shows
two peaks at m/z 576.0 and 496.0 for the ions corresponding
Results and Discussion
Synthesis of Copper(I) Complexes
Treatment of thioether aminophosphonites 2a and 2b to [M+ – (2a + CuBr)] and [M+ – (2a + CuBr2)], respec-
with one equivalent of CuX (X = Cl, Br, and I) in dichloro- tively. Spectroscopic studies on complexes 4a and 6b could
methane/acetonitrile mixtures leads to the formation of the not be carried out because of their poor solubility in most
halide-bridged dinuclear CuI complexes [{[{-OC10H6(µ-S)- organic solvents; however, their chemical compositions
C10H6O-}PNC4H8E-κP]Cu(µ-X)}2] (4a: E = O, X = Cl; 4b: were established by elemental analysis. The molecular struc-
E = NMe, X = Cl; 5a: E = O, X = Br; 5b: E = NMe, X = ture of complex 5a was confirmed by a single-crystal X-ray
Br; 6a: E = O, X = I; 6b: E = NMe, X = I) in good yields, diffraction study.
Scheme 2.
Eur. J. Inorg. Chem. 2007, 720–731
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The reactions of 2a with CuX (X = Cl, Br, and I) in a despite these centers being in close proximity [P···S non-
2:1 ratio in dichloromethane afford the tricoordinate mono- bonding distances in 2a and 2b are 3.089(1) and 3.040(1) Å,
nuclear complexes [{[-OC10H6(µ-S)C10H6O-]PNC4H8O- respectively].[7] However, the P,S-chelated cationic com-
κP}2CuX] (7a: X = Cl; 8a: X = Br; 9a: X = I; Scheme 2). plexes [{[-OC10H6(µ-S)C10H6O-]PNC4H8O-κP,κS}2Cu]BF4
The 31P NMR spectra of complexes 7a, 8a, and 9a show (10a)
and
[{[-OC10H6(µ-S)C10H6O-]PNC4H8NCH3-
single resonances at δ = 115.8, 112.3, and 111.8 ppm, κP,κS}2Cu]BF4 (10b) are formed when ligands 2a and 2b
1
respectively. In the H NMR spectra of these complexes, are treated with half an equivalent of [Cu(MeCN)4]BF4, as
two broad singlets are observed in the region δ = 3.29– shown in Scheme 2. Both these complexes are moderately
3.66 ppm for the CH2 protons of the morpholine moiety, stable in the solid state but decompose slowly in solution.
although two distinct triplets (δ = 3.41 and 3.79 ppm) are The 31P NMR spectra of complexes 10a and 10b show sin-
observed for ligand 2a. Similarly, the reactions of 2b with gle resonances at δ = 112.2 and 113.7 ppm, respectively. The
half an equivalent of CuX (X = Cl, Br, and I) produce mass spectrum of complex 10a shows peaks at m/z 929.1
the mononuclear complexes [{[-OC10H6(µ-S)C10H6O-] and 496.0 for the ions [M+ – BF4] and [M+ – (2a + BF4)],
PNC4H8NCH3-κP}2CuX] (7b: X = Cl; 8b: X = Br; 9b: X respectively. Similarly, for complex 10b peaks are observed
= I) in good yields The chloro and bromo derivatives pre- at m/z 955.2 and 509.1 for the ions [M+ – BF4] and [M+
cipitate during the course of reaction while the iodo deriva- (2b + BF4)], respectively.
tive crystallizes from the mother liquor. The 31P NMR spec-
–
tra of complexes 7b, 8b, and 9b show single resonances at δ
= 112.2, 113.4, and 116.9 ppm, respectively. Further sup-
Synthesis of Silver(I) Complexes
port for the structural composition of these complexes
1
comes from their H NMR spectra and elemental analyses,
Treatment of thioether aminophosphonites 2a and 2b
while single-crystal X-ray structure determinations estab- with one equivalent of AgOTf gives complexes with the
lished the structures of complexes 7a and 8a. composition [(2a)Ag(OTf)] (11a) and [(2b)Ag(OTf)] (11b),
Surprisingly, ligands 2a and 2b in the above complexes respectively. These complexes are highly light sensitive in
(4a–9b) are monodentate with only phosphorus coordina- solution, whereas they are moderately stable in the solid
tion and do not form chelate rings with the P and S centers state. In the room-temperature 31P NMR spectrum of com-
Scheme 3.
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Group 11 Complexes of Thioether Aminophosphonites
FULL PAPER
plex 11b, two broad resonances separated by about 594 Hz This may be due to the bulkiness of the ligand, with the
are observed centered at δ = 123.3 ppm, while one broad closeness of the sulfur atom to the gold center (vide infra)
singlet is observed at δ = 118.8 ppm for complex 11a. Pre- preventing another ligand from approaching the gold cen-
vious 31P NMR studies of phosphane and phosphite com- ter. The 31P NMR spectra of complexes 13a and 13b show
plexes of AgI salts involving both coordinating and nonco- single resonances at δ = 113.1 and 115.3 ppm, respectively.
ordinating anions[6d,10] have shown the existence of ligand When these complexes are treated with CuI in dichloro-
dissociation and/or exchange processes at or below room methane at room temperature, they undergo halide ex-
temperature that lead to broad resonances due to the loss change to form the iodo derivatives [{[-OC10H6(µ-S)-
1
of the expected JAg,P couplings. Typically, the low-tem- C10H6O-]PNC4H8E-κP}AuI] (14a: E = O; 14b: E = NMe).
perature limiting spectra consist of two doublets for each The 31P NMR spectra of complexes 14a and 14b show sing-
group of chemically equivalent phosphorus nuclei due to lets at δ = 118.1 and 118.9 ppm, which are considerably
coupling with both 109Ag and 107Ag. Unfortunately, due to deshielded compared to their chloro analogs. The molecular
the poor solubility and stability of 11a and 11b, low-tem- compositions of these complexes (13a,b and 14a,b) were
perature NMR studies could not be carried out, so that further confirmed by their 1H NMR spectra, elemental
while with 11a there is probably only one phosphorus envi- analysis data, and X-ray diffraction studies for complexes
ronment, in the case of 11b it is not clear whether there are 13a, 13b, and 14a. Other groups have also reported similar
two different phosphorus environments or simply one halogen-exchange reactions of gold complexes with KI at
where the dynamic process occurring is sufficiently slow elevated temperature,[12] although halogen exchange of
that an average 1JAg,P coupling is observed. Structural stud- gold(I) complexes with CuI is not known in the literature.
ies of the silver complexes of another P,S ligand
[Fc(PPh2)(SPh)] show a preference for a four-coordinate
tetrahedral geometry.[6d] Although only tentatively because
of the limited data available, we suggest that complexes 11a
and 11b contain a chelating P,S ligand and are either mono-
Crystals Structures of Complexes 5a, 7a, 8a, 13a, 13b, and
14a
meric with a bidentate trifluoromethanesulfonate or dinu-
Perspective views of the molecular structures of com-
clear with bridging trifluoromethanesulfonate ligands. Simi- pounds 5a, 7a, 8a, 13a, 13b, and 14a with the atom-number-
larly, the P,S chelated complexes [{[-OC10H6(µ-S)C10H6O-]- ing schemes are shown in Figures 1, 2, 3, 4, 5, and 6, respec-
PNC4H8E-κP,κS}Ag(PPh3)]CF3SO3 (12a: E = O; 12b: E = tively. Selected bond lengths and bond angles for complexes
NMe) can be synthesized by treatment of 2a and 2b with 5a, 7a, and 8a appear in Table 1, whereas those of com-
[Ag(PPh3)][OTf] in a 1:1 molar ratio. The 31P NMR spec- plexes 13a, 13b, and 14a are listed in Table 2. Crystal data
trum of complex 12a shows two sets of broad doublets cen- and the details of the structure determinations are given in
1
tered at δ = 123.9 and 9.7 ppm with JAg,P coupling con- the Experimental Section.
stants of about 512 and 394 Hz for coordinated 2a and
In the molecular structure of complex 5a, each of the
PPh3, respectively. However, the 31P NMR spectrum of copper centers is coordinated to one phosphorus center and
complex 12b shows broad singlets at δ = 130.3 and 8.2 ppm two bromine atoms and exists as a centrosymmetric dimer.
for coordinated 2b and PPh3, respectively. In the mass spec- The morpholine rings adopt a chair conformation and the
tra of complexes 12a and 12b, peaks are observed at m/z sulfur atoms connecting the naphthalene groups face
803.1 and 816.9, respectively, for the ion [M+ – CF3SO3]. towards the Cu2Br2 ring with a Cu···S separation of
By analogy with the complex [Ag(PPh3){Fc(PPh2)- 3.0901(14) Å. As this is less than the sum of the van der
(SPh)}(OTf)],[6d] which contains a chelating P,S ligand and Waals radii for copper and sulfur (3.20 Å),[13] there may be
coordinated triflate, we propose that 12a and 12b are mono- a weak Cu···S interaction. The backbones of two amino-
meric, four-coordinate species with chelating P,S ligands phosphonite ligands are in the staggered conformation,
and monodentate trifluoromethanesulfonate. Further sup- while the PCu(µ-Br)2CuP unit is almost planar. Several tri-
port for the composition of these complexes comes from gonal planar dinuclear copper complexes of this type con-
their 1H NMR spectra and elemental analysis data taining monophosphanes have been well characterized,[14]
(Scheme 3).
however those of aminophosphonites or phosphites are
rare. The Cu–P bond length [2.171(1) Å] in complex 5a is
comparable with that in the tetrahedral copper complex of
the monophosphite 4-nitro,2,6,7-trioxa-1-phosphabicyclo-
[2.2.2]octane [Cu–P 2.1683(6) Å].[15] The Cu···Cu and
Synthesis of Gold(I) Complexes
The reactions of thioether aminophosphonites 2a and 2b Br···Br distances are 3.108 and 3.758 Å, respectively, indi-
with [AuCl(SMe2)] in dichloromethane afford the mononu- cating a possible weak Cu···Cu interaction. The core angles
clear P-coordinated complexes [{[-OC10H6(µ-S)C10H6O-]- Cu–Br–Cua [79.17(2)°] and Br–Cu–Bra [100.83(2)°] are sig-
PNC4H8E-κP}AuCl] (13a: E = O; 13b: E = NMe). Both nificantly distorted from those of the above-mentioned
complexes are white, crystalline solids and are light sensitive monophosphite complex [Cu–Br–Cua 75.183(12); Br–Cu–
while in solution. Attempt to synthesize three-coordinate Bra 104.817(12)°].[15]
gold complexes akin to [(PPh3)2AuCl][11] were unsuccessful
and resulted in the formation of complexes 13a and 13b. weak coordinative interaction with phosphorus, as indi-
Interestingly, the sulfur atom also appears to show a
Eur. J. Inorg. Chem. 2007, 720–731
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B. Punji, J. T. Mague, M. S. Balakrishna
FULL PAPER
Figure 1. Molecular structure of 5a. All hydrogen atoms have been omitted for clarity. Displacement ellipsoids are drawn at the 50%
probability level.
Figure 3. Molecular structure of 8a. Solvent molecules and all hy-
drogen atoms have been omitted for clarity. Displacement ellipsoids
are drawn at the 50% probability level.
Figure 2. Molecular structure of 7a·CH2Cl2. Solvent molecules and
all hydrogen atoms have been omitted for clarity. Displacement el-
lipsoids are drawn at the 50% probability level.
radii (2.12 Å). For complex 5a the %TBP displacement is
cated by the P···S distance [3.098(2) Å]. This P···S distance calculated to be 36.1% (Table 3).
is comparable to that observed in our previous report[7] and
The molecular structures of the chloride (7a) and bro-
that of others[16] (see Table 3). While considerably greater mide (8a) complexes are isomorphous; they crystallize in
than the sum of the covalent radii for sulfur and phospho- the monoclinic space group P21/n. In both structures the
rus (2.12 Å),[17] this distance is less than the sum of van der copper centers are coordinated through two aminophos-
Waals radii (3.65 Å)[13] for these two elements. This interac- phonite ligands and a halide ion and exist as monomers.
tion leads to the structural displacement of phosphorus The geometries around the copper center are almost planar.
from pyramidal to a pseudo TBP. The degree to which the The Cu–P bond lengths in complex 7a [Cu–P1 2.2062, Cu–
TBP is approached can be seen from the axial S–P–R angle P2 2.1897(7) Å] and complex 8a [Cu–P1 2.1884(6), Cu–P2
and can be quantified by the procedure of Holmes and co- 2.2063(5) Å] are almost identical. As seen in complex 5a,
workers.[18] In this procedure, the degree of displacement the sulfur atoms in complexes 7a and 8a show coordinative
from pyramidal toward TBP can be calculated by noting interaction towards the phosphorus centers [7a: S1–P1
how far the P···S distance departs from the sum of the van 3.088(1), S2–P2 3.199(1) Å; 8a: S1–P1 3.1918(8), S2–P2
der Waals radii (3.65 Å) toward the sum of the covalent 3.0874(8) Å], which forces the phosphorus centers to as-
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Group 11 Complexes of Thioether Aminophosphonites
FULL PAPER
Figure 4. Molecular structure of 13a. All hydrogen atoms have been
omitted for clarity. Displacement ellipsoids are drawn at the 50%
probability level.
Figure 5. Molecular structure of 13b. All hydrogen atoms have been
omitted for clarity. Displacement ellipsoids are drawn at the 50%
probability level.
sume pseudo TBP geometries (Table 3). Although the sulfur sum of the van der Waals radii. The P1–Cu–P2 bond angle
atoms in both complexes are pointing towards the copper in bromo derivative 8a [130.20(2)°] is slightly greater than
center, no sulfur to copper bonding interaction is observed that of the chloro complex 7a [128.61(3)°]. Structural data
as the Cu···S separations are 0.17–0.42 Å greater than the are available for a number of three-coordinate complexes of
Table 1. Selected bond lengths [Å] and bond angles [°] for complexes 5a, 7a, and 8a. Symmetry operation: _a: 0.5 – x, 0.5 + y, 0.5 – z.
5a
7a
8a
Br–Cu
Br–Cu_a
Cu–P
S–C10
S–C20
P–O1
P–O2
P–N
Cu–Br–Cu_a
Br–Cu–P
Br–Cu–Br_a
Br_a–Cu–P
C10–S–C20
Cu–P–O1
Cu–P–O2
2.3828(9)
2.4931(9)
2.171(1)
1.793(5)
1.792(4)
1.632(3)
1.663(3)
1.639(4)
79.17(2)
142.15(4)
100.83(2)
116.96(4)
102.8(2)
110.9(1)
120.2(1)
Cu–Cl1
Cu–P1
Cu–P2
S1–C2
S1–C12
P1–O2
P1–O1
P1–N1
Cl1–Cu–P1
Cl1–Cu–P2
P1–Cu–P2
C2–S1–C12
C26–S2–C36
Cu–P1–O1
Cu–P1–O2
Cu–P1–N1
2.2307(8)
2.2062(8)
2.1897(7)
1.774(2)
1.768(2)
1.636(2)
1.650(2)
1.631(2)
Br–Cu
Cu–P1
Cu–P2
S1–C2
S1–C12
P1–O2
P1–O1
P1–N1
Br–Cu–P1
Br–Cu–P2
P1–Cu–P2
C2–S1–C12
C26–S2–C36
Cu–P1–O1
Cu–P1–O2
Cu–P1–N1
2.3374(4)
2.1884(6)
2.2063(5)
1.772(2)
1.773(2)
1.637(1)
1.645(2)
1.636(2)
116.73(3)
114.13(2)
114.66(3)
128.61(3)
102.2(1)
115.66(2)
130.20(2)
102.68(9)
102.46(9)
115.52(6)
120.95(5)
115.99(7)
102.7(1)
114.07(7)
124.53(7)
113.80(8)
Table 2. Selected bond lengths [Å] and bond angles [°] for complexes 13a, 13b, and 14a.
13a
13b
14a
Au–Cl
Au–P
S–C6
S–C16
P–O1
P–O2
P–N
2.2725(7)
2.2002(7)
1.776(2)
1.783(2)
1.611(2)
1.618(2)
1.628(2)
Au–Cl
Au–P
S–C2
S–C12
P–O1
P–O2
P–N1
2.2786(5)
2.2038(5)
1.775(2)
1.781(2)
1.612(1)
1.618(1)
1.630(2)
Au–I
Au–P
S–C10
S–C11
P–O1
P–O2
P–N
2.5603(3)
2.2291(8)
1.780(3)
1.773(3)
1.634(3)
1.618(2)
1.621(3)
Cl–Au–P
C6–S–C16
Au–P–O1
Au–P–O2
Au–P–N
O1–P–O2
178.73(2)
101.3(1)
117.17(7)
117.07(8)
114.44(8)
100.78(8)
Cl–Au–P
C2–S–C12
Au–P–O1
Au–P–O2
Au–P–N1
O1–P–O2
176.67(2)
I–Au–P
C10–S–C11
Au–P–O1
Au–P–O2
Au–P–N
O1–P–O2
170.41(2)
100.54(8)
116.93(5)
117.57(5)
112.70(6)
101.12(7)
102.8(2)
111.36(9)
119.69(9)
117.8(1)
99.9(1)
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725

B. Punji, J. T. Mague, M. S. Balakrishna
FULL PAPER
Table 3. (continued)
Figure 6. Molecular structure of 14a. All hydrogen atoms have been
omitted for clarity. Displacement ellipsoids are drawn at the 50%
probability level.
the type [CuX(PR3)2] containing tertiary phosphanes[14] but
analogous complexes containing aminophosphonites or
phosphites are not present in the literature.
Table 3. Comparison of P–S bond parameters and ring conforma-
tions obtained from the X-ray studies for cyclic phosphites (in in-
creasing order of %TBP).
[a] Percent geometrical displacement from a pyramid towards a
TBP. [b] With reference to a TBP with sulfur in an axial site.
726
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Group 11 Complexes of Thioether Aminophosphonites
FULL PAPER
For complexes 13a and 13b the unit cell contains two action with the metal. Structurally characterized dinuclear
molecules arranged in an anti-parallel manner with no trigonal-planar copper complexes of phosphites or amino-
intermolecular gold–gold interaction [a common feature phosphonites of the type 5a are rare. Silver and cationic
among linear mononuclear gold(I) complexes][12b] present copper complexes (10a and 10b) have also been synthesized
(Au···Au 5.017 and 5.511 Å, respectively). The Au–Cl where sulfur is also involved in coordination. Gold com-
[2.2725(7) and 2.2786(5) Å] and Au–P bond lengths plexes of both the thioether aminophosphonite ligands un-
[2.2002(7) and 2.2038(5) Å] in complexes 13a and 13b are dergo halide exchange with copper(I) iodide to form the
comparable with those observed for [(PhO)3PAuCl] [Au–Cl iodide derivatives in quantitative yield at room temperature.
2.273(5), Au–P 2.192(5) Å][19a] as well as for [{2,4,6- Generally, the halogen-exchange reactions of platinum
tBu3C6H2P=C(Cl)PPh2}AuCl] [Au–Cl 2.283(1), Au–P metal derivatives are carried out at high temperature using
2.229(1) Å].[19b] The S···Au separations observed in 13a and an excess of NaI or KI. In all the complexes, the sulfur
13b are 3.4876(6) and 3.4508(5) Å, respectively, which are atom present in the eight-membered mesocycle shows a ten-
comparable to the sum of the van der Waals radii for gold dency to coordinate to phosphorus. As a consequence, the
and sulfur (3.46 Å).[13] There is thus only a minimal Au···S tricoordinate geometry of phosphorus is displaced towards
interaction at best. As with the previous complexes, the sul- TBP.
fur atoms in 13a and 13b show a coordinative interaction
towards phosphorus, with S···P separations of 3.1820(8)
(for 13a) and 3.1673(7) Å (for 13b), which are markedly
shorter than the sum of the van der Waals radii for sulfur
and phosphorus (3.65 Å).[13] The geometries around gold
are not quite linear, with Cl–Au–P bond angles of
178.73(2)° and 176.67(2)°, respectively, for 13a and 13b.
Again, these are comparable with that found in [(PhO)3-
PAuCl] [Cl–Au–P 178.5(2)°].[19a]
Experimental Section
Reagents and Technique: All experimental manipulations were car-
ried out under an atmosphere of dry nitrogen or argon using
Schlenk techniques. Solvents were dried and distilled prior to use
by conventional methods. The thioether aminophosphonites (2a
and 2b) were prepared as reported previously.[7] The metal precur-
sors CuX (X = Cl and Br),[22] [Cu(MeCN)4]BF4,[23] [AuCl-
(SMe2)][24] and [Ag(OTf)PPh3][25] were prepared according to the
published procedures. The 1H and 31P{1H} NMR spectra (δ in
ppm) were obtained with a Varian VXR 300 or VRX 400 spectrom-
eter operating at frequencies of 300 or 400 (1H) and 121 or
162 MHz (31P), respectively. The spectra were recorded for CDCl3
(or [D6]DMSO or [D6]acetone) solutions with CDCl3 (or [D6]-
DMSO or [D6]acetone) as an internal lock; TMS and 85% H3PO4
The molecular structure of complex 14a is shown in Fig-
ure 6. The unit cell contains two molecules that are some-
what more closely packed (Au···Au 4.285 Å) than is ob-
served for the chloro derivative 13a. The Au–P bond
[2.2291(8) Å] is somewhat longer than that found in the
chloro derivative 13a, possibly reflecting the increased size
and polarizability of iodine compared with chlorine. The
sulfur shows weak interactions with the gold and phospho-
rus centers since the S···Au and S···P distances [3.2976(9)
and 3.1566(13) Å, respectively] are less than the sum of the
van der Waals radii (S···Au 3.46 and S···P 3.65 Å).[13] There
is a C–H···I contact of 3.075 Å with a C17–H17–I angle of
139.82°. As this distance lies between the outer limits pro-
posed by Steiner[20] and by Brammer et al.[21] for C–H···I
hydrogen bonds, and as the C–H···I angle is rather small,
this is a weak interaction at best. The coordination about
the gold center is less linear, with an I–Au–P bond angle of
170.41(2)°.
were used as internal and external standards for H and 31P{1H}
1
NMR, respectively. Positive shifts lie downfield of the standard in
all cases. IR spectra were recorded with a Nicolet Impact 400 FTIR
instrument as KBr disks. Microanalyses were carried out with a
Carlo–Erba Model 1106 elemental analyzer. Q-Tof Micromass ex-
periments were carried out with a Waters Q-Tof micro (YA-105).
Melting points of all compounds were determined with a Veego
melting point apparatus and are uncorrected.
Synthesis of [{[{-OC10H6(µ-S)C10H6O-}PNC4H8O-κP]Cu(µ-Cl)}2]
(4a): A solution of 2a (0.087 g, 0.202 mmol) in dichloromethane
(10 mL) was added dropwise to a solution of CuCl (0.02 g,
0.202 mmol) in acetonitrile (4 mL) and the reaction mixture was
stirred for 1 h. The white precipitate formed was filtered and dried
under vacuum. Yield: 85% (0.091 g); m.p. 208 °C (dec.).
C48H40Cl2Cu2N2O6P2S2 (1064.9): calcd. C 54.14, H 3.79, N 2.63,
S 6.02; found C 54.08, H 3.75, N 2.61, S 5.97.
Conclusions
Synthesis of [{[{-OC10H6(µ-S)C10H6O-}PNC4H8NCH3-κP]Cu(µ-
Cl)}2] (4b): This compound was synthesized by a procedure similar
to that for 4a from 2b (0.090 g, 0.202 mmol) and CuCl (0.02 g,
0.202 mmol). Yield: 83% (0.091 g); m.p. 186 °C (dec.).
C50H46Cl2Cu2N4O4P2S2 (1091.0): calcd. C 55.04, H 4.25, N 5.14,
S 5.88; found C 54.98, H 4.22, N 5.11, S 5.81. 1H NMR (400 MHz,
[D6]DMSO): δ = 8.62 (d, 3JH,H = 8.8 Hz, 4 H, ArH), 7.92 (d, 3JH,H
= 8.4 Hz, 8 H, ArH), 7.22–7.65 (m, 12 H, ArH), 3.33 (br. s, 8 H,
CH2), 2.49 (br. s, 8 H, CH2), 2.06 (s, 6 H, CH3) ppm. 31P{1H}
NMR (162 MHz, [D6]DMSO): δ = 114.4 (s) ppm.
Group 11 metal complexes of thioether aminophos-
phonite ligands have been synthesized. The aminophos-
phonites 2a and 2b, which contain a hemilabile thioether
functionality, show versatile coordination properties. By
choosing appropriate metal reagents and reaction condi-
tions both mono- and chelating bidentate modes of coordi-
nation can be achieved. With copper halides both the mo-
nonuclear and dinuclear trigonal planar complexes are ob-
tained. In these complexes only phosphorus takes part in
coordination, leaving the sulfur center uncoordinated. The
uncoordinated sulfur atom is pointing towards the metal
Synthesis of [{[{-OC10H6(µ-S)C10H6O-}PNC4H8O-κP]Cu(µ-Br)}2]
(5a): This compound was synthesized by a procedure similar to
center in all complexes, and in some cases there is an inter- that for 4a from 2a (0.06 g, 0.139 mmol) and CuBr (0.02 g,
Eur. J. Inorg. Chem. 2007, 720–731
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727

B. Punji, J. T. Mague, M. S. Balakrishna
FULL PAPER
0.139 mmol). Yield: 85% (0.068 g); m.p. 228 °C (dec.).
C48H40Br2Cu2N2O6P2S2 (1153.8): calcd. C 49.97, H 3.49, N 2.43,
S 5.56; found C 49.92, H 3.45, N 2.41, S 5.51. 1H NMR (400 MHz,
that for 7a from CuBr (0.015 g, 0.105 mmol) and 2a (0.093 g,
0.214 mmol). Yield: 90% (0.104 g); m.p. 242 °C (dec.).
C48H40BrCuN2O6P2S2·CH2Cl2 (1095.30): calcd. C 53.73, H 3.87,
3
3
[D6]DMSO): δ = 8.67 (d, JH,H = 8.4 Hz, 4 H, ArH), 7.97 (t, JH,H
N 2.56, S 5.86; found C 53.65, H 3.82, N 2.51, S 5.82. 1H NMR
3
3
= 9.2 Hz, 8 H, ArH), 7.67 (d, JH,H = 6.8 Hz, 4 H, ArH), 7.51 (d, (400 MHz, [D6]DMSO): δ = 8.71 (d, JH,H = 8.8 Hz, 4 H, ArH),
3
3JH,H = 6.8 Hz, 4 H, ArH), 7.37 (d, JH,H = 8.4 Hz, 4 H, ArH),
7.26–8.01 (m, 20 H, ArH), 3.65 (br. s, 8 H, CH2), 3.31 (br. s, 8 H,
3.71 (br. s, 8 H, CH2), 3.37 (br. s, 8 H, CH2) ppm. 31P{1H} NMR CH2) ppm. 31P{1H} NMR (162 MHz, [D6]DMSO): δ = 112.3 (s)
(162 MHz, [D6]DMSO): δ = 113.3 (s) ppm. MS (EI): m/z 576.0
[M+ – (L + CuBr)], 496.0 [M+ – (L + CuBr2)].
ppm.
Synthesis of [{[-OC10H6(µ-S)C10H6O-]PNC4H8NCH3-κP}2CuBr]
(8b): This compound was synthesized by a procedure similar to
that for 7a from CuBr (0.015 g, 0.105 mmol) and 2b (0.096 g,
0.214 mmol) and was stirred for 4 h. Yield: 85% (0.092 g); m.p.
196 °C (dec.). C50H46BrCuN4O4P2S2 (1036.5): calcd. C 57.94, H
4.47, N 5.41, S 6.19; found C 57.89, H 4.41, N 5.36, S 6.10. 1H
NMR (400 MHz, [D6]DMSO): δ = 8.63 (d, JH,H = 8.4 Hz, 4 H,
ArH), 7.92 (d, JH,H = 8.8 Hz, 8 H, ArH), 7.33–7.66 (m, 12 H,
ArH), 3.34 (br. s, 8 H, CH2), 2.52 (br. s, 8 H, CH2), 2.09 (s, 6 H,
CH3) ppm. 31P{1H} NMR (121.4 MHz, [D6]DMSO): δ = 113.4 (s)
ppm.
Synthesis of [{[{-OC10H6(µ-S)C10H6O-}PNC4H8NCH3-κP]Cu(µ-
Br)}2] (5b): This compound was synthesized by a procedure similar
to that for 4a from 2b (0.062 g, 0.139 mmol) and CuBr (0.02 g,
0.139 mmol). Yield: 83% (0.068 g); m.p. 196 °C (dec.).
C50H46Br2Cu2N4O4P2S2 (1179.9): calcd. C 50.89, H 3.93, N 4.75,
S 5.44; found C 50.82, H 3.89, N 4.71, S 5.42. 1H NMR (400 MHz,
[D6]DMSO): δ = 8.75 (d, 3JH,H = 8.8 Hz, 4 H, ArH), 7.05 (d, 3JH,H
= 8.4 Hz, 4 H, ArH), 7.36–7.99 (m, 16 H, ArH), 3.37 (br. s, 8 H,
CH2), 2.50 (br. s, 8 H, CH2), 2.29 (s, 6 H, CH3) ppm. 31P{1H}
NMR (162 MHz, [D6]DMSO): δ = 110.5 (s) ppm.
3
3
Synthesis of [{[{-OC10H6(µ-S)C10H6O-}PNC4H8O-κP]Cu(µ-I)}2]
(6a): This compound was synthesized by a procedure similar to
that for 4a from 2a (0.068 g, 0.157 mmol) and CuI (0.03 g,
0.157 mmol) and was stirred for 2 h. Yield: 89% (0.087 g); m.p.
232 °C (dec.). C48H40Cu2I2N2O6P2S2 (1247.8): calcd. C 46.20, H
3.23, N 2.24, S 5.14; found C 46.15, H 3.21, N 2.22, S 5.11. 1H
Synthesis of [{[-OC10H6(µ-S)C10H6O-]PNC4H8O-κP}2CuI] (9a):
This compound was synthesized by a procedure similar to that for
7a from CuI (0.02 g, 0.105 mmol) and 2a (0.093 g, 0.215 mmol)
and was stirred for 6 h. Yield: 81% (0.09 g); m.p. 220 °C (dec.).
C48H40CuIN2O6P2S2 (1057.4): calcd. C 54.52, H 3.81, N 2.65, S
1
6.07; found C 54.49, H 3.78, N 2.62, S 5.98. H NMR (400 MHz,
3
[D6]DMSO): δ = 8.71 (d, 3JH,H = 8.8 Hz, 4 H, ArH), 8.02 (d, 3JH,H
NMR (400 MHz, [D6]DMSO): δ = 8.67 (d, JH,H = 8.4 Hz, 4 H,
3
3
ArH), 7.96 (t, JH,H = 7.2 Hz, 8 H, ArH), 7.39–7.67 (m, 12 H,
= 8.4 Hz, 4 H, ArH), 7.96 (d, JH,H = 8.0 Hz, 4 H, ArH), 7.31–
ArH), 3.71 (br. s, 8 H, CH2), 3.35 (br. s, 8 H, CH2) ppm. 31P{1H}
7.91 (m, 12 H, ArH), 3.66 (br. s, 8 H, CH2), 3.29 (br. s, 8 H, CH2)
ppm. 31P{1H} NMR (121.4 MHz, [D6]DMSO): δ = 111.8 (s) ppm.
NMR (162 MHz, [D6]DMSO): δ = 110.4 (s) ppm.
Synthesis of [{[{-OC10H6(µ-S)C10H6O-}PNC4H8NCH3-κP]Cu(µ-
I)}2] (6b): This compound was synthesized by a procedure similar
to that for 4a from 2b (0.07 g, 0.157 mmol) and CuI (0.03 g,
0.157 mmol). Yield: 88% (0.088 g); m.p. 192 °C (dec.).
C50H46Cu2I2N4O4P2S2 (1273.9): calcd. C 47.14, H 3.64, N 4.39, S
5.03; found C 47.03, H 3.57, N 4.32, S 4.98.
Synthesis of [{[-OC10H6(µ-S)C10H6O-]PNC4H8NCH3-κP}2CuI]
(9b): This compound was synthesized by a procedure similar to that
for 7a from CuI (0.02 g, 0.105 mmol) and 2b (0.096 g, 0.215 mmol).
Yield: 83% (0.095 g); m.p. 232 °C (dec.). C50H46CuIN4O4P2S2
(1083.5): calcd. C 55.43, H 4.28, N 5.17, S 5.92; found C 55.38, H
4.27, N 5.15, S 5.88. 1H NMR (400 MHz, [D6]DMSO): δ = 8.71
(d, 3JH,H = 8.4 Hz, 4 H, ArH), 7.76 (d, 3JH,H = 8.0 Hz, 4 H, ArH),
Synthesis of [{[-OC10H6(µ-S)C10H6O-]PNC4H8O-κP}2CuCl] (7a):
CuCl (0.01 g, 0.101 mmol) was added to a solution of 2a (0.09 g,
0.207 mmol) in dichloromethane (12 mL) and the reaction mixture
was stirred for 3 h. The colorless solution obtained was concen-
trated (5 mL) under vacuum and 1 mL of acetonitrile was added.
Slow evaporation of the solution at room temperature gave color-
less crystals of 7a. Yield: 88% (0.093 g); m.p. 218 °C (dec.).
C48H40ClCuN2O6P2S2·CH2Cl2 (1050.9): calcd. C 56.00, H 4.03, N
2.67, S 6.10; found C 55.96, H 4.01, N 2.59, S 5.96. 1H NMR
3
3
7.64 (d, JH,H = 9.2 Hz, 4 H, ArH), 7.61 (t, JH,H = 8.0 Hz, 4 H,
3
3
ArH), 7.44 (t, JH,H = 7.2 Hz, 4 H, ArH), 6.94 (d, JH,H = 8.4 Hz,
4 H, ArH), 3.47 (br. s, 8 H, CH2), 2.49 (br. s, 8 H, CH2), 2.13 (s,
6 H, CH3) ppm. 31P{1H} NMR (162 MHz, [D6]DMSO): δ = 116.9
(s) ppm.
Synthesis of [{[-OC10H6(µ-S)C10H6O-]PNC4H8O-κP,κS}2Cu]BF4
(10a): [Cu(MeCN)4]BF4 (0.025 g, 0.079 mmol) was added to a solu-
tion of 2a (0.07 g, 0.162 mmol) in dichloromethane (15 mL) and
the reaction mixture was stirred for 2 h. The resultant solution was
concentrated to 5 mL under vacuum and layered with petroleum
ether (1 mL) to give 10a as a white crystalline product at –25 °C.
Yield: 89% (0.072 g); m.p. 170–172 °C (dec.). C48H40BCuF4-
N2O6P2S2 (1017.3): calcd. C 56.67, H 3.96, N 2.75, S 6.30; found
3
(400 MHz, [D6]DMSO): δ = 8.60 (d, JH,H = 8.4 Hz, 4 H, ArH),
3
3
7.89 (d, JH,H = 8.8 Hz, 8 H, ArH), 7.62 (t, JH,H = 7.2 Hz, 4 H,
3
3
ArH), 7.45 (t, JH,H = 7.2 Hz, 4 H, ArH), 7.23 (d, JH,H = 8.8 Hz,
4 H, ArH), 3.64 (br. s, 8 H, CH2), 3.30 (br. s, 8 H, CH2) ppm.
31P{1H} NMR (121.4 MHz, [D6]DMSO): δ = 115.8 (s) ppm.
1
C 56.59, H 3.92, N 2.73, S 6.26. H NMR (400 MHz, CDCl3): δ =
Synthesis of [{(-OC10H6(µ-S)C10H6O-)PNC4H8NCH3-κP}2CuCl]
(7b): This compound was synthesized by a procedure similar to
that for 7a from 2b (0.092 g, 0.207 mmol) and CuCl (0.01 g,
0.101 mmol). Yield: 87% (0.087 g); m.p. 188 °C (dec.).
C50H46ClCuN4O4P2S2 (992.00): calcd. C 60.54, H 4.67, N 5.65, S
3
3
8.52 (d, JH,H = 7.6 Hz, 4 H, ArH), 7.77 (d, JH,H = 8.4 Hz, 8 H,
ArH), 7.26–7.54 (m, 8 H, ArH), 7.12 (d, 3JH,H = 8.0 Hz, 4 H, ArH),
3.74 (br. s, 8 H, CH2), 3.37 (br. s, 8 H, CH2) ppm. 31P{1H} NMR
(121.4 MHz, CDCl3): δ = 112.2 (s) ppm. MS (EI): m/z 929.1 [M+
BF4], 496.0 [M+ – (L + BF4)].
–
1
6.46; found C 60.49, H 4.63, N 5.61, S 6.40. H NMR (400 MHz,
[D6]DMSO): δ = 8.65 (d, 3JH,H = 7.6 Hz, 4 H, ArH), 7.95 (d, 3JH,H
Synthesis of [{[-OC10H6(µ-S)C10H6O-]PNC4H8NCH3-κP,κS}2-
Cu]BF4 (10b): This compound was synthesized by a procedure sim-
ilar to that for 10a from 2b (0.072 g, 0.162 mmol) and [Cu(MeCN)4]-
BF4 (0.025 g, 0.079 mmol). Yield: 90% (0.075 g); m.p. 158–160 °C
(dec.). C50H46BCuF4N4O4P2S2 (1043.35): calcd. C 57.56, H 4.44,
3
= 8.4 Hz, 8 H, ArH), 7.67 (t, JH,H = 8.4 Hz, 4 H, ArH), 7.50 (t,
3
3JH,H = 8.4 Hz, 4 H, ArH), 7.31 (d, JH,H = 7.6 Hz, 4 H, ArH),
3.33 (br. s, 8 H, CH2), 2.50 (br. s, 8 H, CH2), 2.08 (s, 6 H, CH3)
ppm. 31P{1H} NMR (162 MHz, [D6]DMSO): δ = 112.2 (s) ppm.
Synthesis of [{[-OC10H6(µ-S)C10H6O-]PNC4H8O-κP}2CuBr] (8a): N 5.37, S 6.15; found C 57.48, H 4.41, N 5.32, S 6.09. 1H NMR
3
This compound was synthesized by
a
procedure similar to
(400 MHz, CDCl3): δ = 8.55 (d, JH,H = 8.4 Hz, 4 H, ArH), 7.59
728
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Eur. J. Inorg. Chem. 2007, 720–731

Group 11 Complexes of Thioether Aminophosphonites
(d, 3JH,H = 8.0 Hz, 8 H, ArH), 6.88–7.56 (m, 12 H, ArH), 3.35 (br. CDCl3): δ = 8.77 (d, JH,H = 8.4 Hz, 2 H, ArH), 7.63–7.87 (m, 6
FULL PAPER
3
3
3
s, 8 H, CH2), 2.52 (br. s, 8 H, CH2), 2.01 (s, 6 H, CH3) ppm.
H, ArH), 7.51 (t, JH,H = 7.2 Hz, 2 H, ArH), 7.24 (d, JH,H =
31P{1H} NMR (162 MHz, CDCl3): δ = 113.7 (s) ppm. MS (EI): 8.0 Hz, 2 H, ArH), 3.84 (t, 3JH,H = 4.8 Hz, 4 H, CH2), 3.65 (t, 3JH,H
m/z 955.2 [M+ – BF4], 509.1 [M+ – (L + BF4)].
= 5.2 Hz, 4 H, CH2) ppm. 31P{1H} NMR (121.4 MHz, CDCl3): δ
= 113.1 (s) ppm.
Synthesis
of [{[{-OC10H6(µ-S)C10H6O-}PNC4H8O-κP,κS]Ag-
(CF3SO3)}2] (11a): AgOTf (0.04 g, 0.156 mmol) was added to a
solution of 2a (0.067 g, 0.156 mmol) in dichloromethane (12 mL)
and the reaction mixture was stirred for 3 h. The resultant solution
was concentrated to 3 mL under vacuum and petroleum ether
(5 mL) was added to precipitate 11a as a white crystalline product,
which was then filtered off and dried under high vacuum. Yield:
91% (0.097 g); m.p. 138 °C (dec.). C25H20AgF3NO6PS2 (690.39):
Synthesis of [{[-OC10H6(µ-S)C10H6O-]PNC4H8NCH3-κP}AuCl]
(13b): This was synthesized by a procedure similar to that for 13a
from 2b (0.053 g, 0.119 mmol) and [AuCl(SMe2)] (0.035 g,
0.119 mmol). Yield: 89% (0.072 g); m.p. 158 °C (dec.).
C25H23AuClN2O2PS (678.92): calcd. C 44.23, H 3.41, N 4.13, S
1
4.72; found C 44.18, H 3.37, N 4.09, S 4.69. H NMR (400 MHz,
[D6]acetone): δ = 8.84 (d, 3JH,H = 8.0 Hz, 2 H, ArH), 8.08 (d, 3JH,H
3
calcd. C 43.49, H 2.92, N 2.03, S 9.29; found C 43.41, H 2.89, N
= 8.8 Hz, 2 H, ArH), 7.99 (d, JH,H = 8.0 Hz, 2 H, ArH), 7.52–
3
1.99, S 9.21. 1H NMR (400 MHz, CDCl3): δ = 8.79 (d, JH,H
=
3
7.76 (m, 4 H, ArH), 7.49 (d, JH,H = 7.6 Hz, 2 H, ArH), 3.72 (br.
8.4 Hz, 2 H, ArH), 7.15–8.32 (m, 10 H, ArH), 3.91 (br. s, 4 H,
CH2), 3.28 (br. s, 4 H, CH2) ppm. 31P{1H} NMR (121.4 MHz,
CDCl3): δ = 118.8 (br. s) ppm.
s, 4 H, CH2), 2.91 (br. s, 4 H, CH2), 2.37 (s, 3 H, CH3) ppm.
31P{1H} NMR (121.4 MHz, [D6]acetone): δ = 115.3 (s) ppm.
Synthesis of [{[-OC10H6(µ-S)C10H6O-]PNC4H8O-κP}AuI] (14a): A
solution of CuI (0.014 g, 0.075 mmol) in acetonitrile (5 mL) was
added dropwise to a solution of 13a (0.05 g, 0.075 mmol) in dichlo-
romethane (8 mL) and the reaction mixture was stirred for 3 h. The
solution obtained was concentrated to 5 mL to give a crystalline
product on cooling to –25 °C. Yield: 74% (0.042 g); m.p. 208–
210 °C (dec.). C24H20AuINO3PS (757.33): calcd. C 38.06, H 2.66,
N 1.85, S 4.23; found C 37.98, H 2.63, N 1.81, S 4.19. 1H NMR
Synthesis of [{[{-OC10H6(µ-S)C10H6O-}PNC4H8NCH3-κP,κS]Ag-
(CF3SO3)}2] (11b): This compound was synthesized by a procedure
similar to that for 11a from 2b (0.069 g, 0.156 mmol) and AgOTf
(0.04 g, 0.156 mmol). Yield: 89% (0.097 g); m.p. 192 °C (dec.).
C26H23AgF3N2O5PS2 (703.44): calcd. C 44.39, H 3.29, N 3.98, S
1
9.12; found C 44.31, H 3.22, N 3.91, S 9.03. H NMR (400 MHz,
3
3
CDCl3): δ = 8.52 (d, JH,H = 8.8 Hz, 4 H, ArH), 8.28 (d, JH,H
=
3
8.4 Hz, 8 H, ArH), 6.86–7.58 (m, 12 H, ArH), 3.19 (br. s, 8 H,
(400 MHz, CDCl3): δ = 8.78 (d, JH,H = 8.0 Hz, 2 H, ArH), 7.43–
CH2), 2.67 (br. s, 8 H, CH2), 2.33 (s, 6 H, CH3) ppm. 31P{1H}
3
7.81 (m, 8 H, ArH), 7.28 (d, JH,H = 8.4 Hz, 2 H, ArH), 3.85 (br.
1
s, 4 H, CH2), 3.68 (br. s, 4 H, CH2) ppm. 31P{1H} NMR (162 MHz,
NMR (162 MHz, CDCl3): δ = 123.3 (2 br. s, JAg,P ≈ 594 Hz, 2 P)
ppm.
CDCl3): δ = 118.1 (s) ppm.
Synthesis
of
[{[-OC10H6(µ-S)C10H6O-]PNC4H8O-κP,κS}Ag-
Synthesis of [{[-OC10H6(µ-S)C10H6O-]PNC4H8NCH3-κP}AuI]
(14b): This complex was synthesized by a procedure similar to that
for 14a from CuI (0.014 g, 0.075 mmol) and 13b (0.051 g,
0.075 mmol). Yield: 69% (0.04 g); m.p. 192–194 °C (dec.).
C25H23AuIN2O2PS (770.37): calcd. C 38.98, H 3.01, N 3.64, S 4.16;
found C 38.92, H 2.97, N 3.59, S 4.12. 1H NMR (400 MHz,
CDCl3): δ = 8.76 (d, 3JH,H = 8.4 Hz, 2 H, ArH), 7.80–7.85 (m, 4 H,
ArH), 7.64 (t, 3JH,H = 7.6 Hz, 2 H, ArH), 7.48 (t, 3JH,H = 7.6 Hz, 2
(PPh3)]CF3SO3 (12a): [Ag(PPh3)][OTf] (0.05 g, 0.096 mmol) was
added to a solution of 2a (0.042 g, 0.096 mmol) in dichloromethane
(12 mL), and the reaction mixture was stirred for 2 h. The solution
was concentrated under vacuum and diethyl ether (5 mL) was
added to precipitate a white crystalline product. This was filtered
off and dried under vacuum. Yield: 82% (0.075 g); m.p. 140–142 °C
(dec.). C43H35AgF3NO6P2S2 (952.69): calcd. C 54.21, H 3.70, N
1.47, S 6.73; found C 54.16, H 3.64, N 1.44, S 6.69. 1H NMR
3
H, ArH), 7.22 (d, JH,H = 8.8 Hz, 2 H, ArH), 3.67 (br. s, 4 H,
3
CH2), 2.55 (br. s, 4 H, CH2), 2.39 (s, 3 H, CH3) ppm. 31P{1H}
(400 MHz, CDCl3): δ = 8.76 (d, JH,H = 8.4 Hz, 2 H, ArH), 7.09–
8.34 (m, 10 H, ArH, 15 H, PPh3), 3.89 (br. s, 4 H, CH2), 3.24 (br.
s, 4 H, CH2) ppm. 31P{1H} NMR (121.4 MHz, CDCl3): δ = 123.9
(2 br. d, JAg,P ≈ 512 Hz, 1 P), 9.7 (2 br. d, JAg,P ≈ 394 Hz, 1 P,
PPh3) ppm. MS (EI): m/z 803.1 [M+ – OTf].
NMR (162 MHz, CDCl3): δ = 118.9 (s) ppm.
X-ray Crystallography: Crystals of 5a, 7a, 8a, 13a, 13b, and 14a
were mounted in a Cryoloop with a drop of Paratone oil and
placed in the cold nitrogen stream of the Kryoflex attachment of
a Bruker APEX CCD diffractometer. A full sphere of data was
collected using 606 scans in ω (0.3° per scan) at φ = 0, 120, and
240° (for 5a, 7a, and 14a) or 400 scans in ω (0.5° per scan) at φ =
0, 90, and 180° plus 800 scans in φ (0.45° per scan) at ω = 0 and
210° (for 8a, 13a, and 13b) using the SMART software package.[26]
The raw data were reduced to F2 values using the SAINT+ soft-
ware[27] and global refinements of unit cell parameters using 4630–
9050 reflections chosen from the full data sets were performed.
Multiple measurements of equivalent reflections provided the basis
for empirical absorption corrections as well as corrections for any
crystal deterioration during the data collection (SADABS[28]). The
structures were solved by direct methods (for 5a, 7a, 8a, 13a, and
13b) or the position of the metal atoms was obtained from a sharp-
ened Patterson function (for 14a) and refined by full-matrix least-
squares procedures using the SHELXTL program package.[29] Hy-
drogen atoms were placed in calculated positions and included as
riding contributions with isotropic displacement parameters tied to
those of the attached non-hydrogen atoms. Pertinent crystallo-
graphic data and other experimental details are summarized in
Tables 4 and 5.
Synthesis of [{[-OC10H6(µ-S)C10H6O-]PNC4H8NCH3-κP,κS}Ag-
(PPh3)]CF3SO3 (12b): This complex was synthesized by a pro-
cedure similar to that for 12a from 2b (0.0043 g, 0.096 mmol) and
[Ag(PPh3)][OTf] (0.05 g, 0.096 mmol). Yield: 78% (0.073 g); m.p.
144 °C (dec.). C44H38AgF3N2O5P2S2 (965.73): calcd. C 54.72, H
3.97, N 2.90, S 6.64; found C 54.68, H 3.92, N 2.88, S 6.59. 1H
3
NMR (400 MHz, CDCl3): δ = 8.64 (d, JH,H = 8.4 Hz, 2 H, ArH),
7.04–7.75 (m, 10 H, ArH, 15 H, PPh3), 3.45 (br. s, 4 H, CH2), 2.61
(br. s, 4 H, CH2), 2.36 (s, 3 H, CH3) ppm. 31P{1H} NMR
(162 MHz, CDCl3): δ = 130.3 (br. s, 1 P), 8.2 (br. s, 1 P, PPh3) ppm.
MS (EI): m/z 816.9 [M+ – OTf].
Synthesis of [{[-OC10H6(µ-S)C10H6O-]PNC4H8O-κP}AuCl] (13a):
A solution of 2a (0.051 g, 0.119 mmol) in CH2Cl2 (8 mL) was
added dropwise to a dichloromethane (5 mL) solution of [AuCl-
(SMe2)] (0.035 g, 0.119 mmol) and the reaction mixture was stirred
for 3 h at room temperature. The solution was concentrated to
3 mL and layered with petroleum ether to give colorless crystals of
13a on cooling to –25 °C. Yield: 90% (0.071 g); m.p. 178–180 °C
(dec.). C24H20AuClNO3PS (665.88): calcd. C 43.29, H 3.03, N 2.10,
S 4.82; found C 43.19, H 2.99, N 2.08, S 4.79. 1H NMR (400 MHz,
Eur. J. Inorg. Chem. 2007, 720–731
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
729

B. Punji, J. T. Mague, M. S. Balakrishna
FULL PAPER
Table 4. Crystallographic data for complexes 5a, 7a, and 8a.
5a
7a
8a
Formula
Molecular weight
Crystal system
Crystal size [mm]
Space group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
C48H40Br2Cu2N2O6P2S2
1153.80
triclinic
C48H40ClCuN2O6P2S2·CH2Cl2
C48H40BrCuN2O6P2S2·CH2Cl2
1050.83
monoclinic
0.17ϫ0.17ϫ0.32
P21/n (no. 14)
13.638(1)
21.690(2)
16.002(2)
90
103.633(2)
90
4600.1(8)
4
1095.26
monoclinic
0.14ϫ0.15ϫ0.28
P21/n (no. 14)
13.582(1)
21.839(2)
16.042(1)
90
103.437(1)
90
4628.1(7)
4
0.11ϫ0.11ϫ0.14
¯
P1 (no. 2)
9.574(2)
11.357(2)
11.462(2)
98.769(2)
108.777(2)
101.580(2)
1123.8(4)
1
γ [°]
V [Å3]
Z
ρcalcd [gcm–3]
µ(Mo-Kα) [mm–1]
F(000)
1.705
2.941
1160
1.517
0.863
2160
1.572
1.663
2232
Temp. [K]
θmin,max [°]
GOF (F2)
100
2.4, 28.4
0.99
0.0504
0.1371
100
2.2, 28.2
1.03
0.0444
0.1220
100
2.4, 28.3
1.04
0.0352
0.0931
[a]
R1
[b]
wR2
2
2 2
[a] R1 = Σ|Fo| – |Fc|/Σ|Fo|. [b] wR2 = {Σw[(Fo – Fc ) ]/Σ[w(Fo2)2]}1/2
.
Table 5. Crystallographic data for complexes 13a, 13b, and 14a.
13a
13b
14a
Formula
Molecular weight
Crystal system
Crystal size [mm]
Space group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
C24H20AuClNO3PS
665.86
triclinic
C25H23AuClN2O2PS
678.90
triclinic
C24H20AuINO3PS
757.32
triclinic
0.09ϫ0.14ϫ0.21
0.14ϫ0.17ϫ0.21
0.12ϫ0.15ϫ0.22
¯
¯
¯
P1 (no. 2)
P1 (no. 2)
P1 (no. 2)
9.9857(9)
10.817(1)
11.704(1)
76.089(1)
67.262(1)
71.899(1)
1097.8(2)
2
9.945(1)
10.500(1)
13.220(1)
103.775(1)
95.073(1)
104.354(1)
1282.9(2)
2
9.5688(8)
11.2775(9)
11.648(1)
99.422(1)
99.004(1)
106.991(1)
1157.7(2)
2
γ [°]
V [Å3]
Z
ρcalcd [gcm–3]
µ(Mo-Kα) [mm–1]
F(000)
2.014
7.019
644
1.757
6.006
660
2.172
7.874
716
Temp. [K]
θmin,max [°]
GOF (F2)
100
2.6, 28.3
1.05
0.0164
0.0399
100
2.9, 28.3
1.05
0.0141
0.0356
100
2.3, 28.2
1.05
0.0236
0.0568
[a]
R1
[b]
wR2
2
2 2
[a] R1 = Σ|Fo| – |Fc|/Σ|Fo|. [b]wR2 = {Σw[(Fo – Fc ) ]/Σ[w(Fo2)2]}1/2
.
CCDC-622054 (for 5a), -622055 (for 7a), -622056 (for 8a), -622057 ana Board of Regents through grant LEQSF(2002-03)-ENH-TR-
(for 13a), -622058 (for 13b), and -622059 (for 14a) contain the sup-
plementary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
67 for funds to purchase the CCD diffractometer and the Chemis-
try Department of Tulane University for support of the X-ray labo-
ratory.
[1] a) P. Braunstein, F. Naud, Angew. Chem. Int. Ed. 2001, 40,
680–699; b) A. M. Masdeu-Bultó, M. Diéguez, E. Martin, M.
Gómez, Coord. Chem. Rev. 2003, 242, 159–201; c) H. Chen, Y.
Liu, S. Peng, S. Liu, Dalton Trans. 2003, 1419–1424; d) D. S.
McGuinness, P. Wasserscheid, D. H. Morgan, J. T. Dixon, Or-
ganometallics 2005, 24, 552–556; e) M. C. Aragoni, M. Arca,
A. Bencini, A. J. Blake, C. Caltagirone, A. Decortes, F. Demar-
tin, F. A. Devillanova, E. Faggi, L. S. Dolci, A. Garau, F. Isaia,
V. Lippolis, L. Prodi, C. Wilson, B. Valtancoli, N. Zaccheroni,
Dalton Trans. 2005, 2994–3004.
Acknowledgments
We are grateful to the Department of Science and Technology
(DST), New Delhi, for funding through grant SR/S1/IC-05/2003.
B. P. thanks the Council of Scientific and Industrial Research
(CSIR), India, for a Senior Research Fellowship (SRF). We also
thank SAIF, Mumbai, Department of Chemistry Instrumentation
Facilities, Bombay, for spectral and analytical data and the Louisi-
730
www.eurjic.org
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 720–731

Group 11 Complexes of Thioether Aminophosphonites
FULL PAPER
[2] For recent example of P,O ligands, see: a) N. Oberbeckmann-
Winter, X. Morise, P. Braunstein, R. Welter, Inorg. Chem. 2005,
44, 1391–1403; b) C. Muller, L. J. Ackerman, J. N. H. Reek,
P. C. J. Kamer, P. W. N. M. van Leeuwen, J. Am. Chem. Soc.
2004, 126, 14960–14963; c) F. Goettmann, D. Grosso, F. Merc-
ier, F. Mathey, C. Sanchez, Chem. Commun. 2004, 1240–1241;
d) W. Dai, Y. Li, Y. Zhang, K. W. Lai, J. Wu, Tetrahedron Lett.
2004, 45, 1999–2001; e) P. Braunstein, B. T. Heaton, C. Jacob,
L. Manzi, X. Morise, Dalton Trans. 2003, 1396–1401.
[3] For recent example of P,N ligands, see: a) R. J. Kloetzing, P.
Knochel, Tetrahedron: Asymmetry 2006, 17, 116–123; b) F.
Speiser, P. Braunstein, L. Saussine, Dalton Trans. 2004, 1539–
1545; c) W. Tang, W. Wang, X. Zhang, Angew. Chem. Int. Ed.
2003, 42, 943–946; d) G. Chelucci, G. Orru, G. A. Pinna, Tetra-
hedron 2003, 59, 9471–9515; e) P. Braunstein, J. Zhang, R. Wel-
ter, Dalton Trans. 2003, 507–509; f) T. Bunlaksananusorn, K.
Polborn, P. Knochel, Angew. Chem. Int. Ed. 2003, 42, 3941–
3943.
[4] For recent example of P,S ligands, see: a) O. Piechaczyk, M.
Doux, L. Ricard, P. Le Floch, Organometallics 2005, 24, 1204–
1213; b) H. Liang, S. Ito, M. Yoshifuji, Org. Lett. 2004, 6,
425–427; c) A. Dervisi, R. L. Jenkins, K. M. A. Malik, M. B.
Hursthouse, S. Coles, Dalton Trans. 2003, 1133–1142; d) M.
Doux, N. Mézailles, M. Melaimi, L. Ricard, P. Le Floch,
Chem. Commun. 2002, 1566–1567; e) J. R. Dilworth, N. Wheat-
ley, Coord. Chem. Rev. 2000, 199, 89–158; f) X. Verdaguer, A.
Moyano, M. A. Pericas, A. Riera, M. A. Maestro, J. Mahia, J.
Am. Chem. Soc. 2000, 122, 10242–10243; g) D. Morales-Mo-
rales, R. Redón, Y. Zheng, J. R. Dilworth, Inorg. Chim. Acta
2002, 328, 39–44; h) J. R. Dilworth, D. Morales-Morales, Y.
Zheng, J. Chem. Soc., Dalton Trans. 2000, 3007–3015.
M. S. Balakrishna, Organometallics 2005, 24, 3780–3783; e) P.
Chandrasekaran, J. T. Mague, M. S. Balakrishna, Inorg. Chem.
2005, 44, 7925–7932; f) P. Chandrasekaran, J. T. Mague, M. S.
Balakrishna, Inorg. Chem. 2006, 45, 5893–5897; g) P. Chandra-
sekaran, J. T. Mague, M. S. Balakrishna, Inorg. Chem. 2006,
45, 6678–6683; h) B. Punji, M. S. Balakrishna, Indian J. Chem.
2006, 45A, 1390–1394.
[9] a) S. Priya, M. S. Balakrishna, S. M. Mobin, R. McDonald, J.
Organomet. Chem. 2003, 688, 227–235; b) S. Mohanty, B.
Punji, M. S. Balakrishna, Polyhedron 2006, 25, 815–820; c) B.
Punji, J. T. Mague, M. S. Balakrishna, Dalton Trans. 2006,
1322–1330; d) B. Punji, C. Ganesamoorthy, M. S. Balakrishna,
J. Mol. Catal. A 2006, 259, 78–83; e) B. Punji, J. T. Mague,
M. S. Balakrishna, J. Organomet. Chem. 2006, 691, 4265–4272.
[10] E. L. Muetterties, C. W. Alegranti, J. Am. Chem. Soc. 1972, 94,
6386–6391.
[11] G. A. Bowmaker, J. C. Dyason, P. C. Healy, L. M. Engelhardt,
C. Pakawatchai, A. H. White, J. Chem. Soc., Dalton Trans.
1987, 1089–1097.
[12] a) T. L. Stott, M. O. Wolf, B. O. Patrick, Inorg. Chem. 2005,
44, 620–627; b) H. Xiao, Y. Weng, W. Wong, T. C. W. Mak, C.
Che, J. Chem. Soc., Dalton Trans. 1997, 221–226; c) H. Schmid-
baur, A. Wohlleben, F. Wagner, O. Orama, G. Huttner, Chem.
Ber. 1977, 110, 1748–1754.
[13] A. Bondi, J. Phys. Chem. 1964, 68, 441–451.
[14] G. A. Bowmaker, S. E. Boyd, J. V. Hanna, R. D. Hart, P. C.
Healy, B. W. Skelton, A. H. White, J. Chem. Soc., Dalton Trans.
2002, 2722–2730.
[15] J. R. Cole, M. E. Dellinger, T. J. Johnson, B. A. Reinecke, R. D.
Pike, W. T. Pennington, M. Krawiec, A. L. Rheingold, J. Chem.
Crystallogr. 2003, 33, 341–347.
[5] a) J. R. Dilworth, C. A. M. von Beckh Widmanstetter, S. I. Pa- [16] a) D. J. Sherlock, A. Chandrasekaran, R. O. Day, R. R.
scu, Dalton Trans. 2005, 2151–2161; b) X. Verdaguer, M. A.
Pericas, A. Riera, M. A. Maestro, J. Mahia, Organometallics
2003, 22, 1868–1877; c) D. Enders, R. Peters, J. Runsink, J. W.
Bats, Org. Lett. 1999, 1, 1863–1866; d) A. Albinati, P. S. Prego-
sin, K. Wick, Organometallics 1996, 15, 2419–2421; e) P. Bar-
baro, A. Currao, J. Herrmann, R. Nesper, P. S. Pregosin, R.
Salzmann, Organometallics 1996, 15, 1879–1888; f) E. Guimet,
M. Diéguez, A. Ruiz, C. Claver, Tetrahedron: Asymmetry 2005,
16, 959–963; g) E. Guimet, M. Diéguez, A. Ruiz, C. Claver,
Dalton Trans. 2005, 2557–2562; h) M. Dieguez, O. Pamies, C.
Claver, Tetrahedron: Asymmetry 2005, 16, 3877–3880; i) D. A.
Holmes, Inorg. Chem. 1997, 36, 5082–5089; b) D. J. Sherlock,
A. Chandrasekaran, R. O. Day, R. R. Holmes, J. Am. Chem.
Soc. 1997, 119, 1317–1322.
[17] L. Sutton, Tables of Interatomic Distances and Configuration,
in Molecules and Ions, Special Publication Nos. 11 and 18, The
Chemical Society, London, 1958 and 1965.
[18] R. O. Day, T. K. Prakasha, R. R. Holmes, H. Eckert, Organo-
metallics 1994, 13, 1285–1293.
[19] a) P. B. Hitchcock, P. L. Pye, J. Chem. Soc., Dalton Trans. 1977,
1457–1460; b) M. Freytag, S. Ito, M. Yoshifuji, Chem. Asian J.
2006, 1, 693–700.
Evans, K. R. Campos, J. S. Tedrow, F. E. Michael, M. R. [20] T. Steiner, Acta Crystallogr., Sect. B 1998, 54, 456–463.
Gagne, J. Org. Chem. 1999, 64, 2994–2995; j) D. A. Evans, F. E.
Michael, J. S. Tedrow, K. R. Campos, J. Am. Chem. Soc. 2003,
125, 3534–3543; k) O. Pamies, M. Diéguez, G. Net, A. Ruiz,
C. Claver, Organometallics 2000, 19, 1488–1496; l) K. Selvaku-
mar, M. Valentini, P. S. Pregosin, A. Albinati, Organometallics
1999, 18, 4591–4597.
[21] L. Brammer, E. A. Bruton, P. Sherwood, Cryst. Growth Des.
2001, 1, 277–290.
[22] B. S. Furniss, A. J. Hannaford, P. W. G. Smith, A. R. Tatchell,
Vogel’s Textbook of Practical Organic Chemistry, Fifth Edition,
ELBS, England, 1989, p. 428–429.
[23] R. A. Heintz, J. A. Smith, P. S. Szalay, A. Weisgerber, K. R.
Dunbar, K. Beck, D. Coucouvanis, Inorg. Synth. 2002, 33, 75–
83.
[24] M. C. Brandys, M. C. Jennings, R. J. Puddephatt, J. Chem.
Soc., Dalton Trans. 2000, 4601–4606.
[25] M. Bardaji, O. Crespo, A. Laguna, A. K. Fischer, Inorg. Chim.
Acta 2000, 304, 7–16.
[26] Bruker-AXS, SMART, Version 5.625, Madison, WI, 2000.
[27] Bruker-AXS, SAINT+, Version 6.35A, Madison, WI, 2002.
[28] G. M. Sheldrick, SADABS, Version 2.05, University of
Göttingen, Germany 2002.
[6] a) M. Doux, L. Ricard, P. Le Floch, N. Mézailles, Dalton
Trans. 2004, 2593–2600; b) M. Diéguez, O. Pamies, G. Net, A.
Ruiz, C. Claver, J. Mol. Catal. A 2002, 185, 11–16; c) S. Cab-
rera, R. G. Arrayas, J. C. Carretero, J. Am. Chem. Soc. 2005,
127, 16394–16395; d) J. E. Aguado, S. Canales, M. C. Gimeno,
P. G. Jones, A. Laguna, M. D. Villacampa, Dalton Trans. 2005,
3005–3015; e) N. Mezailles, L. Ricard, F. Gagosz, Org. Lett.
2005, 7, 4133–4136.
[7] B. Punji, J. T. Mague, M. S. Balakrishna, Inorg. Chem. 2006,
45, 9454–9464.
[8] a) M. S. Balakrishna, R. Panda, J. T. Mague, Inorg. Chem.
2001, 40, 5620–5625; b) M. S. Balakrishna, R. Panda, J. T.
Mague, J. Chem. Soc., Dalton Trans. 2002, 4617–4621; c) S.
Priya, M. S. Balakrishna, J. T. Mague, S. M. Mobin, Inorg.
Chem. 2003, 42, 1272–1281; d) P. Chandrasekaran, J. T. Mague,
[29] a) Bruker-AXS, SHELXTL, Version 6.10, Madison, WI, 2000;
b) G. M. Sheldrick, SHELXS97 and SHELXL97, University
of Göttingen, Germany 1997.
Received: September 26, 2006
Published Online: December 19, 2006
Eur. J. Inorg. Chem. 2007, 720–731
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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