Organometallic nickel(II) complexes with dithiophosphate, dithiophosphonate and monothiophosphonate ligands

Article abstract of DOI:10.1016/j.ica.2003.06.013

The hydroxo complex [NBu₄]₂[Ni₂(C ₆F₅)₄(μ-OH)₂] reacts with ammonium O,σ-dialkyldithiophosphates, O-alkyl-p- methoxyphenyldithiophosphonate acids and ammonium O- alkylferrocenyldithiophosphonates in dichloromethane under mild conditions to give, respectively, [NBu₄][Ni(C₆F₅) ₂{S(S)P(OR)₂}] (R=Me (1), Et (2), ⁱPr (3)) and [NBu₄][Ni(C₆F₅)₂{S(S)P(OR)Ar}] (Ar=p-MeOC₆H₄, R=Me (4), Et (5), ⁱPr (6); Ar=ferrocenyl; R=Me (7), Et (8), ⁱPr (9)). The monothiophosphonate nickel complexes [NBu₄][Ni(C₆F₅) ₂{S(S)P(OR)(ferrocenyl)}] (R=Et (10), ⁱPr (11)) are obtained by reaction of the hydroxo complex with O- alkylferrocenyldithiophosphonate acids. Analytical (C, H, N, S), conductivity, and spectroscopic (IR, ¹H, ¹⁹F and ³¹P NMR, and FAB-MS) data were used for structural assignments. A single-crystal X-ray diffraction study of [NBu₄][Ni(C₆F₅) ₂{S(S)P(OMe)(p-MeOC₆H₄)}] (4) and [NBu ₄][Ni(C₆F₅)₂{S(O)P(OEt)(ferrocenyl)} ] (10) shows that in both cases the coordination around the nickel atom es essentially square planar with NiC₂S₂ and NiC ₂SO central cores, respectively.

Full text of DOI:10.1016/j.ica.2003.06.013

Inorganica Chimica Acta 357 (2004) 677–683
www.elsevier.com/locate/ica
Organometallic nickel(II) complexes with dithiophosphate,
dithiophosphonate and monothiophosphonate ligands
a
Gregorio Sanchez , Joaquın Garcıa , David J. Meseguer , Jose L. Serrano ,
a
a
b
ꢀ
ꢀ
ꢀ
Jose Perez , Elıes Molins , Gregorio Lopez
ꢀ
b
c
a,
*
ꢀ ꢀ
ꢀ
ꢀ
a
ꢀ
ꢀ
Departamento de Quımica Inorganica, Universidad de Murcia, 30071 Murcia, Spain
b
Departamento de Ingenierꢀıa Minera, Geoloꢀgica y Cartograꢀfica (Area de Quꢀımica Inorgaꢀnica),
Universidad Politeꢀcnica de Cartagena, 30230 Cartagena, Spain
c
Institut de Cieꢁncia de Materials, CSIC, Camps Universitari de Bellaterra, 08193 Cerdanyola, Spain
Received 9 April 2003; accepted 11 June 2003
Abstract
The hydroxo complex [NBu4]2[Ni2(C6F5)4(l-OH)2] reacts with ammonium O; O0-dialkyldithiophosphates, O-alkyl-p-methoxy-
phenyldithiophosphonate acids and ammonium O-alkylferrocenyldithiophosphonates in dichloromethane under mild conditions
i
to give, respectively, [NBu4][Ni(C6F5)2{S(S)P(OR)2}] (R ¼ Me (1), Et (2), Pr (3)) and [NBu4][Ni(C6F5)2{S(S)P(OR)Ar}] (Ar ¼ p-
i
i
MeOC6H4, R ¼ Me (4), Et (5), Pr (6); Ar ¼ ferrocenyl; R ¼ Me (7), Et (8), Pr (9)). The monothiophosphonate nickel complexes
[NBu4][Ni(C6F5)2{S(S)P(OR)(ferrocenyl)}] (R ¼ Et (10), iPr (11)) are obtained by reaction of the hydroxo complex with
O-alkylferrocenyldithiophosphonate acids. Analytical (C, H, N, S), conductivity, and spectroscopic (IR, 1H, 19F and 31P NMR, and
FAB-MS) data were used for structural assignments. A single-crystal X-ray diffraction study of [NBu4][Ni(C6F5)2{S(S)P(OMe)(p-
MeOC6H4)}] (4) and [NBu4][Ni(C6F5)2{S(O)P(OEt)(ferrocenyl)}] (10) shows that in both cases the coordination around the nickel
atom es essentially square planar with NiC2S2 and NiC2SO central cores, respectively.
Ó 2003 Elsevier B.V. All rights reserved.
Keywords: Nickel complexes; Dithiophosphate complexes; Dithiophosphonate complexes; Monothiophosphonate complexes
1. Introduction
catalyst precursors for the oligomerization of ethylene
has also been recently reported [10].
Phosphor-1,1-dithiolate-type ligands, which include
the monoanionic dithiophosphates, dithiophosphinates,
and dithiophosphonates (Scheme 1 (a)–(c)), have re-
ceived continuous attention, since they display a wide
variety of coordination modes which leads to a diversity
of molecular and supramolecular structures [1–3]. Fur-
thermore, their metal complexes have been effectively
used as additives in lubrication oils [4–6], and the solu-
bility in organic solvents of many metal derivatives has
allowed to develop extraction procedures [7]. Some of
the organometallic derivatives have been found to dis-
play antitumor activity [8] and others are useful in ag-
riculture as insecticides [9]. The synthesis and
application of dithiophosphinate complexes of nickel as
In contrast to the well documented chemistry of
transition metal complexes with dithiophosphates (a)
and dithiophosphinates (b) [1–3,10,11], synthetic diffi-
culties have prevented a wider use of dithiophospho-
nates (c) as ligands [12,13]. The utilization of the
LawessonÕs reagent [ArP(S)S]2 (Ar ¼ p-MeOC6H4) [14]
and the related ferrocenyl dimer (Ar ¼ ferrocenyl)
to generate dithiophosphonic acids by reaction with
* Corresponding authors. Fax: +34-968-364148.
ꢀ
E-mail address: gll@um.es (G. Lopez).
Scheme 1.
0020-1693/$ - see front matter Ó 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2003.06.013

678
G. Sꢀanchez et al. / Inorganica Chimica Acta 357 (2004) 677–683
alcohols and sylanols [15] under appropriate conditions
pointed out a new route to obtain dithiophosphonate
complexes. Thus, the corresponding ammonium salts,
readily obtained from the acids through reaction with dry
NH3, enabled the preparation of some gold(I) [15] and
platinum(II) derivatives [16]. The ring-opening of the
LawessonÕs reagent was also the key step to prepare ho-
moleptic dithiophosphonate and amidodithiophospho-
nate complexes of nickel, palladium and platinum [17]. In
any case, a nucleophilic agent is required to induce the
ring-opening of the [ArP(S)S]2 dimers. Up till now,
methanol, that acts both as solvent and reagent, and
amines in an inert solvent are the alternatives to achieve
direct reaction with a few metallic precursors [17]. The
previous isolation of the sodium or the above mentioned
ammonium salts, followed by reaction with a convenient
precursor, completes the available routes to synthesise
ditiophosphonate complexes, that for the time being have
not allowed the preparation of organometallic nickel(II)
complexes with di- and monothiophosphonate ligands.
On the other hand, the dinuclear bis(l-hydroxo)
complex [Ni2(C6F5)4(l-OH)2]2ꢀ has shown to be an use-
ful and versatile reagent for the preparation of a wide
variety of complexes, on the basis of the considerable
nucleophilicity of their bridging OH groups. Thus,
compounds of the types [Ni2(C6F5)4(l-X)2]2ꢀ or
[Ni(C6F5)2X]ꢀ (X ¼ exo- or endo-bidentate ligands) have
been obtained by reaction of this precursor with the cor-
responding protic electrophile, HX or (NH4)X, respec-
tively (X ¼ azoles [18], thiols [19], aromatic alcohols [20],
heterocycle-2-thiones [21], anionic N-donor ligands [22]
and thiometallates [23]). In a related reaction, the hy-
droxo complex reacts with primary and secondary amines
in the presence of carbon disulfide to give dithiocarba-
mate complexes [24]. Recently, we have also prepared
some mononuclear organometallic complexes of nick-
el(II) with thiolate and dithiocarbamate ligands [25] as
well as some dithiophosphate and dithiophosphonate
complexes of pentacoordinate nickel(II) [26].
ldithiophosphonates acids [14] and ammonium O-al-
kylferrocenyldithiophosphonates [15] were prepared as
described elsewhere.
C, H, N and S analyses were carried out with a Carlo
Erba instrument. Conductance measurements were per-
formed with a Crison 525 conductimeter (in acetone so-
lution, c ꢁ 5 ꢂ 10ꢀ4 M). Decomposition temperatures
were determined with a Reichert microscope. IR spectra
were recorded on a Perkin–Elmer-16F PC FT spectro-
photometer, using Nujol mulls between polyethylene
sheets. NMR data (1H, 19F, 31P) were recorded on a
Bruker-AC-200E or Varian 300 instrument, using CDCl3
as solvent and SiMe4, CFCl3 or H3PO4 as reference.
2.2. Preparation of the complexes [NBu4][Ni(C6F5)2
{S2P(OR)2}] (1–3)
Ammonium dithiophosphate (0.038 mmol) was added
to a solution of [NBu4]2[Ni2(C6F5)4(l-OH)2] (0.1 g, 0.076
mmol) in dichloromethane (10 ml), and the mixture was
stirred at room temperature for 30 min. It was concen-
trated under reduced pressure to ca. 2 ml. The addition of
diethyl ether caused the precipitation of the title com-
plexes which were separated, washed with diethyl ether
and air-dried. The complexes were recrystallized from
dichloromethane–hexane.
[NBu4][Ni(C6F5)2{S2P(OMe)2}] (1) was obtained in
62% yield. Anal. Calc. for C30H42F10NNiO2PS2: C, 45.5;
H, 5.3; N, 1.8; S, 8.1. Found: C, 45.2; H, 5.4; N, 1.9; S,
8.3%. M.p. 104 °C. KM 115 S cm2 molꢀ1. IR (Nujol):
668, 650 (PS str). 1H NMR (CDCl3): 4.0 (d, 6H, OCH3,
JPH ¼ 10:0). 19F NMR (CDCl3): )115.4 (d, 4Fo, Jom
¼
31:0), )165.9 (t, 2Fp, Jmp ¼ 19:8), )166.6 (m, 4Fm). 31P
NMR (CDCl3): 95.2 (s).
[NBu4][Ni(C6F5)2{S2P(OEt)2}] (2) was obtained in
58% yield. Anal. Calc. for C32H46F10NNiO2PS2: C, 46.8;
H, 5.6; N, 1.7; S, 7.8. Found: C, 46.6; H, 5.8; N, 1.8; S,
8.1%. M.p. 103 °C. KM 132 S cm2 molꢀ1. IR (Nujol): 664,
650 (PS str). 1H NMR (CDCl3): 1.5 (m, 6H, OCH2CH3),
4.4 (m, 4H, OCH2CH3). 19F NMR (CDCl3): )115.3 (d,
4Fo, Jom ¼ 31:04), )165.2 (t, 2Fp, Jmp ¼ 19:8), )166.7 (m,
4Fm). 31P NMR (CDCl3): 90.6 (s).
Following our systematic study of the reactivity shown
by hydroxo complexes of the nickel group elements, we
have now investigated the reactions of [Ni2(C6F5)4(l-
OH)2]2ꢀ with ammonium O; O0-dialkyldithiophosphates,
ammonium O-alkylferrocenyldithiophosphonates and O-
alkylaryldithiophosphonate acids. It has shown to be a
novel and interesting synthetic route to obtain the first
organometallic nickel(II) derivatives with these ligands.
[NBu4][Ni(C6F5)2{S2P(OiPr)2}] (3) was obtained in
72% yield. Anal. Calc. for C34H50F10NNiO2PS2: C, 48.1;
H, 5.9; N, 1.6; S, 7.6. Found: C, 47.8; H, 5.8; N, 1.8; S,
7.8%. M.p. 105 °C. KM 126 S cm2 molꢀ1. IR (Nujol): 644
1
(PS str). H NMR (CDCl3): 1.4 (m, 12H, OCH(CH3)2),
5.3 (m, 2H, OCH(CH3)2). 19F NMR (CDCl3): )115.1 (d,
4Fo, Jom ¼ 29:9), )165.2 (t, 2Fp, Jmp ¼ 20:9, ), )166.6 (m,
4Fm). 31P NMR (CDCl3): 87.4 (s).
2. Experimental
2.1. Materials and physical measurements
2.3. Preparation of the complexes [NBu4][Ni(C6F5)2
{S2P(C6H4OMe-p)(OR)}] (4–6)
All the solvents were dried by conventional methods.
[NBu4]2[Ni2(C6F5)4(l-OH)2] [18], ammonium O; O0-
dialkyldithiophosphate [27], O-alkyl-p-methoxypheny-
5 ml of aliphatic alcohol (ROH) were placed in a flask
with 0.031 g (0.076 mmol) of 2,4-bis(p-methoxyphenyl)-

G. Sꢀanchez et al. / Inorganica Chimica Acta 357 (2004) 677–683
679
1,3-dithiaphosphetane disulfide [LawessonÕs reagent:
(ArP(S)S)2 (Ar ¼ p-MeOC6H4)], and the mixture was
boiled under reflux for 30 min. It was concentrated
under reduced pressure to ca. 2 ml and a solution of
[NBu4]2[Ni2(C6F5)4(l-OH)2] (0.1 g, 0.076 mmol) in di-
chloromethane (10 ml) was then added. The solution
was stirred at room temperature for 30 min and after
that time was concentrated under reduced pressure to
ca. 2 ml. The addition of diethyl ether (15 ml) and
subsequent cooling to )18 °C for 24 h caused the crys-
tallization of the complex. The compounds were filtered
off, washed with diethyl ether and recrystallized from
dichloromethane–hexane.
reduced pressure to ca. 2 ml. Diethyl ether was added to
precipitate an orange solid, which was filtered off and
recrystallized from dichloromethane–hexane.
[NBu4][Ni(C6F5)2{S(S)P(C5H4FeC5H5)(OMe)}] (7)
was obtained in 62% yield. Anal. Calc. for
C39H48F10FeNNiOPS2: C, 49.5; H, 5.1; N, 1.5; S, 6.8.
Found: C, 49.7; H, 5.4; N, 1.7; S, 6.6%. M.p. 124 °C. KM
1
121 S cm2 molꢀ1. IR (Nujol): 648 (PS str). H NMR
(CDCl3): 4.02 (d, 3H, OCH3, JPH ¼ 15:0), 4.38 (br, 2H,
C5H4-P), 4.47 (s, 5H, C5H5), 4.73 (br, 2H, C5H4-P). 19
F
NMR (CDCl3): )114.5 (br, 4Fo), )165.2 (t, 2Fp,
Jmp ¼ 19:7), )166.5 (br, 4Fm). 31P NMR (CDCl3): 104.8
(s).
[NBu4][Ni(C6F5)2{S2P(C6H4OMe-p)(OMe)}] (4) was
[NBu4][Ni(C6F5)2{S(S)P(C5H4FeC5H5)(OEt)}]
(8)
obtained
in
57%
yield.
Anal.
Calc.
for
was obtained in 58% yield. Anal. Calc. for
C40H50F10FeNNiOPS2: C, 50.0; H, 5.2; N, 1.5; S, 6.7.
Found: C, 49.9; H, 5.5; N, 1.6; S, 6.9%. M.p. 128 °C. KM
C36H46F10NNiO2PS2: C, 49.8; H, 5.3; N, 1.6; S, 7.4.
Found: C, 50.0; H, 5.4; N, 1.8; S, 7.5%. M.p. 104 °C. KM
138 S cm2 molꢀ1. IR (Nujol): 660, 632 (PS str). 1H
NMR (CDCl3): 3.8 (s, 3H, p-MeOC6H4), 4.0 (d, 3H,
OCH3, JPH ¼ 14:84), 6.9 (m, 2H, p-MeOC6H4), 8.1 (dd,
2H, p-MeOC6H4, JPH ¼ 13:6; JHH ¼ 8:8). 19F NMR
(CDCl3): )114.6 (br, 2Fo), )115.3 (br, 2Fo), )165.3 (t,
2Fp, Jmp ¼ 19:8), )166.7 (m, 4Fm). 31P NMR (CDCl3):
97.0 (s).
1
117 S cm2 molꢀ1. IR (Nujol): 648 (PS str). H NMR
(CDCl3): 1.40 (sh, 3H, CH3), 4.38 (br, 2H, C5H4-P),
4.43–4.56 (m, 7H, C5H5 + CH2O), 4.75 (br, 2H, C5H4-
P). 19F NMR (CDCl3): )114.5 (br, 4Fo), )165.3 (t, 2Fp,
Jmp ¼ 19:5), )166.5 (m, 4Fm). 31P NMR (CDCl3): 100.7
(s).
[NBu4][Ni(C6F5)2{S(S)P(C5H4FeC5H5)(OiPr)}] (9)
was obtained in 65% yield. Anal. Calc. for
C41H52F10FeNNiOPS2: C, 50.5; H, 5.4; N, 1.4; S, 6.6.
Found: C, 50.2; H, 5.5; N, 1.3; S, 6.8%. M.p. 132 °C. KM
[NBu4][Ni(C6F5)2{S2P(C6H4OMe-p)(OEt)}] (5) was
obtained
in
54%
yield.
Anal.
Calc.
for
C37H48F10NNiO2PS2: C, 50.3; H, 5.5; N, 1.6; S, 7.3.
Found: C, 50.2; H, 5.7; N, 1.8; S, 7.5%. M.p. 112 °C. KM
120 S cm2 molꢀ1. IR (Nujol): 668, 632 (PS str). 1H
NMR (CDCl3): 1.39 (sh, 3H, OEt), 3.8 (s, 3H, p-
MeOC6H4), 4.55 (d, 2H, OEt), 6.9 (m, 2H, p-
MeOC6H4), 7.93 (m, 2H, p-MeOC6H4). 19F NMR
(CDCl3): )114.9 (br, 2Fo), )115.5 (br, 2Fo), )165.4 (t,
2Fp, Jmp ¼ 19:8, ), )166.7 (m, 4Fm). 31P NMR (CDCl3):
93.2 (s).
1
123 S cm2 molꢀ1. IR (Nujol): 652 (PS str). H NMR
(CDCl3): 1.43 (sh, 6H, iPr), 4.38 (m, 7H, C5H4-
P + C5H5), 4.78 (br, 2H, C5H4-P), 5.46 (m, 1H, iPr). 19
F
NMR (CDCl3): )114.5 (d, 4Fo, Jom ¼ 24:8), )165.4 (t,
2Fp, Jmp ¼ 19:8), )166.6 (m, 4Fm). 31P NMR (CDCl3):
96.6 (s).
2.5. Preparation of the complexes [NBu4][Ni(C6F5)2
{S(O)P(C5H4FeC5H5)(OR)}] (10, 11)
[NBu4][Ni(C6F5)2{S2P(C6H4OMe-p)(OiPr)}] (6) was
obtained
in
61%
yield.
Anal.
Calc.
for
C38H50F10NNiO2PS2: C, 50.9; H, 5.6; N, 1.6; S, 7.1.
Found: C, 50.7; H, 5.4; N, 1.8; S, 7.3%. M.p. 122 °C. KM
138 S cm2 molꢀ1. IR (Nujol): 662, 624 (PS str). 1H
NMR (CDCl3): 1.4 (d, 6H, OCH(CH3)2, J ¼ 7:6), 3.8 (s,
3H, p-MeOC6H4), 5.4 (m, 1H, OCH(CH3)2), 6.9 (d, 2H,
p-MeOC6H4, JHH ¼ 8:7), 8.2 (dd, 2H, p-MeOC6H4,
JPH ¼ 13:5, JHH ¼ 8:7). 19F NMR (CDCl3): )114.3 (br,
2Fo), )115.1 (br, 2Fo), )165.3 (t, 2Fp, Jmp ¼ 20:6),
)166.5 (m, 4Fm). 31P NMR (CDCl3): 90.4 (s).
5 ml of aliphatic alcohol (ROH) were placed in a flask
with 0.043 g (0.076 mmol) of 2,4-bis(ferrocenyl)-1,3-
dithiaphosphetane disulfide and the mixture was then
boiled under reflux for 30 min. It was concentrated
under reduced pressure to ca. 2 ml and a solution of
[NBu4]2[Ni2(C6F5)4(l-OH)2] (0.1 g, 0.076 mmol) in di-
chloromethane (10 ml) was then added. The solution
was stirred at room temperature for 24 h and after that
time concentrated under reduced pressure to ca. 2 ml.
The addition of diethyl ether (15 ml) caused the pre-
cipitation of the complexes, that were filtered off, wa-
shed with diethyl ether and air-dried. The complexes
were recrystallized from dichloromethane–hexane.
[NBu4][Ni(C6F5)2{S(O)P(C5H4FeC5H5)(OEt)}] (10)
was obtained in 66% yield. Anal. Calc. for
C40H49F10FeNNiO2PS: C, 50.9; H, 5.2; N, 1.5; S; 3.4.
Found: C, 51.1; H, 5.4; N, 1.8; S, 3.6%. M.p. 133 °C. KM
2.4. Preparation of the complexes [NBu4][Ni(C6F5)2
{S(S)P(C5H4FeC5H5)(OR)}] (7–9)
Ammonium
alkylferrocenyldithiophosphonate,
[NH4] [S(S)P(C5H4FeC5H5)(OR)] (R ¼ Me, Et, iPr),
(0.152 mmol) was added to
a
solution of
[NBu4]2[Ni2(C6F5)4(l-OH)2] (0.1 g, 0.076 mmol) in di-
chloromethane (10 ml). The solution was stirred at room
temperature for 15 min. and then concentrated under
1
128 S cm2 molꢀ1. IR (Nujol): 652 (PS str). H NMR
(CDCl3): 1.36 (sh, 3H, CH3), 4.26 (br, 2H, C5H4-P),

680
G. Sꢀanchez et al. / Inorganica Chimica Acta 357 (2004) 677–683
4.49 (m, 7H, C5H5 + CH2O), 4.56 (br, 2H, C5H4P). 19F
NMR (CDCl3): )114.8 (d, 2Fo, Jom ¼ 27:1), )116.4 (d,
2Fo, Jom ¼ 32:2), )164.4 (t, 1Fp, Jmp ¼ 20:6), )165.3 (t,
1Fp, Jmp ¼ 20:9), )166.5 (m, 4Fm), ), )167.3 (m, 4Fm).
31P NMR (CDCl3): 81.6 (s).
was made in 10 (Tmin ¼ 0:6938 and Tmax ¼ 0:8286). The
structures were solved by direct methods (for 4) and by
Patterson method (for 10) SHELXS-97 [28] and refined
anisotropically on F 2 (program SHELXL-97 [28]). Hy-
drogen atoms were included using a riding model [1].
[NBu4][Ni(C6F5)2{S(O)P(C5H4FeC5H5)(OiPr)}] (11)
was obtained in 68% yield. Anal. Calc. for
C41H52F10FeNNiO2PS: C, 51.4; H, 5.5; N, 1.5; S, 3.3.
Found: C, 51.2; H, 5.7; N, 1.6; S, 3.5%. M.p. 139 °C. KM
3. Results and discussion
1
120 S cm2 molꢀ1. IR (Nujol): 652 (PS str). H NMR
3.1. Dithiophosphate complexes
(CDCl3): 1.37 (sh, 6H, iPr), 4.25 (br, 2H, C5H4-P ), 4.46-
i
4.57 (m, 7H, C5H5 + C5H4-P), 5.54 (m, 1H, Pr). 19F
The addition of the corresponding ammonium O; O0-
dialkyldithiophosphate to a solution of [NBu4]2
[Ni2(C6F5)4(l-OH)2] in dichloromethane results in the
rapid formation of bis(pentafluoropheny)-O; O0-dial-
kyldithiophosphatenickelate(II) complexes 1–3 shown in
Scheme 2. The complexes are isolated as tetrabutylam-
NMR (CDCl3): )114.5 (d, 2Fo, Jom ¼ 27:9), )116.1 (d,
2Fo, Jom ¼ 28:2), )164.6 (t, 1Fp, Jmp ¼ 19:8, ), )165.3 (t,
1Fp, Jmp ¼ 19:8), )166.4 (m, 4Fm), ), )167.2 (m, 4Fm).
31P NMR (CDCl3): 80.5 (s).
2.6. Crystal-structure determination of complexes 4 and
10
Crystals of
4
(0.40 ꢂ 0.30 ꢂ 0.20 mm) and 10
(0.40 ꢂ 0.40 ꢂ 0.10 mm) suitable for X-ray diffraction
studies were grown from dichloromethane–hexane,
mounted on glass fibre and transferred to the diffrac-
tometer (Siemens P4 for 4 and Enraf-Nonius CAD4 for
10). The crystallographic data are summarised in Table
ꢂ
1. Mo-Ka radiation was used (k ¼ 0:71073 A); the scan
method was x ꢀ 2h corresponding to hmax ¼ 25 (in 4)
and hmax ¼ 23:7 (in 10). Absorption correction was not
necessary in 4; empirical psi-scan absorption correction
Scheme 2.
Table 1
Crystal data and parameter of data collection for complexes 4 and 10
4
10
Empirical formula
Formula weight
C
868.54
36H46F10NNiO2PS2
C40H50F10FeNNiO2PS
944.40
293(2)
Temperature (K)
Absorption coefficient (cmꢀ1
Crystal system
173(2)
7.06
)
9.32
monoclinic
P21=n
11.0320(10)
20.484(2)
19.889(2)
105.575(9)
4; 4329.5(7)
1.449
monoclinic
P21=c
Space group
ꢂ
a (A)
ꢂ
11.3270(10)
19.3170(10)
18.7940(10)
102.636(4)
4; 4012.6(5)
1.438
b (A)
ꢂ
c (A)
b (°)
Z; V (A )
3
ꢂ
Calculated density (g cmꢀ3
F(000)
Measured reflections
)
1800
17 320
1952
6674
No. of independent reflections
Observed reflections
Parameters
7066
4377
6322
1927
478
0.0406
514
0.0581
a
R1
wR2
b
0.1064
0.649
0.1058
0.749
Sc
Maximumꢀ, 3minimum
0.425, )0.314
0.437, )0.320
ꢂ
Dq (e A
)
P
P
P
a R1 ¼ kFoj ꢀ jFck= jFoj for reflections with I > 2rI.
P
P
2
2
1=2
2
b wR2 ¼ f ½wðFo2 ꢀ Fc2Þ ꢃ= ½wðFo2Þ ꢃg for all reflections; wꢀ1 ¼ r2ðF 2Þ þ ðaPÞ þ bP, where P ¼ ð2Fc2 þ Fo2Þ=3 and a and b are constants set by
the program.
2
c S ¼ f ½wðFo2 ꢀ Fc2Þ ꢃ=ðn ꢀ pÞg1=2; n is the number of reflections and p the total number of parameters refined.

G. Sꢀanchez et al. / Inorganica Chimica Acta 357 (2004) 677–683
681
monium salts, and they behave as 1:1 electrolytes in
acetone solutions [29]. The IR spectra of these com-
pounds show the characteristic absorptions of the C6F5
ogous bis(pentafluorophenyl)(O-alkylferrocenyldithio-
phosphonate)-nickelate(II) complexes 7–9 were made by
a different synthetic route, that is, treating [NBu4]2
[Ni2(C6F5)4(l-OH)2] with 2 equivalents of ammonium
O-alkylferrocenyldithiophosphonate (Scheme 3). All the
complexes are air-stable orange solids and their acetone
solutions exhibit conductance values corresponding to
1:1 electrolytes [29].
group at ca. 1630 m, 1490 vs., 1050 vs. and 950 vs. cmꢀ1
.
The presence of two bands in the 800–780 cmꢀ1 region
for the so-called ‘‘X-sensitive’’ mode of the C6F5 ligand
is characteristic of the cis-Ni(C6F5)2 fragment [30],
which obviously appears in compounds containing
bidentate chelate ligands. The most relevant IR bands
attributed to the coordinated dithiophosphate ligands
appear in the 1050–960 and 690–630 cmꢀ1 regions [31].
The 1H NMR spectra show the expected aliphatic
signals, and the 19F NMR spectra exhibit the three
signals pattern (4Fo:2Fp:4Fm) usually found in com-
pounds with two equivalent and freely rotating C6F5
groups. The 31P NMR spectra show a single resonance
for the coordinated dithiophosphate ligand at the usual
range. A displacement of the signals downfield as the
aliphatic substituent become smaller is the only re-
markable feature. It has been claimed that the variation
of the S–P–S bond angle affects the 31P chemical shifts,
in the sense that resonances downfield correspond to an
increase in this angle [17,32].
1
The H and 19F NMR data are consistent with the
proposed formulae. The 19F NMR spectra of the new
complexes show three resonances with relative intensi-
ties of 2:1:2, as expected for two equivalent C6F5
groups, while the observed 31P signals follow the trend
mentioned above.
The crystal structure of complex 4 has been deter-
mined by single-crystal X-ray diffraction (Fig. 1). Se-
lected geometrical features are given in Table 2. The
overall coordination geometry about the nickel atom is
essentially square planar. The S1–Ni–S2 angle is
slightly restricted by the chelate ring to 87.37(4)° and the
3.2. Dithiophosphonate complexes
The 2,4-diaryl-1,3-dithiaphosphetane disulfide dimer
[ArP(S)S]2, (Ar ¼ p-C6H4OMe, LawessonÕs reagent)
easily reacts with alcohols (ROH) to form dithiophos-
phonic acids, HSP(S)Ar(OR). Slow addition of a
solution of the hydroxo-complex [NBu4]2[Ni2(C6F5)4(l-
OH)2] in dichloromethane over the dithiophosphonic
acids in alcohol solution leads to the formation of the
O-alkyl-p-methoxyphenyl-dithiophosphonate complexes
4–6 presented in Scheme 3. On the other hand, the anal-
Fig. 1. Structure of the anion of complex 4 in the crystal. Counterca-
tions are Bu4Nþ (not shown).
Table 2
ꢂ
Selected bond lengths (A) and angles (°) for complexes 4 and 10
4
10
Bond lengths
Ni(1)–C(1)
Ni(1)–C(7)
Ni(1)–S(1)
Ni(1)–S(2)
1.913(3)
1.900(4)
Ni(1)–C(1)
Ni(1)–C(7)
Ni(1)–S(1)
Ni(1)–O(2)
1.891(8)
1.844(8)
2.264(2)
1.997(4)
2.2716(10)
2.2712(10)
Bond angles
C(1)–Ni(1)–S(1)
C(7)–Ni(1)–S(1)
C(1)–Ni(1)–C(7)
S(2)–Ni(1)–S(1)
C(1)–Ni(1)–S(2)
C(7)–Ni(1)–S(2)
92.90(11)
176.86(11)
89.04(15)
87.37(4)
C(1)–Ni(1)–S(1)
C(7)–Ni(1)–S(1)
C(1)–Ni(1)–C(7)
O(2)–Ni(1)–S(1)
C(1)–Ni(1)–O(2)
C(7)–Ni(1)–O(2)
175.7(3)
93.6(2)
89.9(3)
81.64(15)
94.8(3)
174.7(3)
179.73(11)
90.69(11)
Scheme 3.

682
G. Sꢀanchez et al. / Inorganica Chimica Acta 357 (2004) 677–683
Ni–C distances are similar to those found in other
pentafluorophenylnickel compounds [19,22,25]. The two
C6F5 rings are planar and rotated from each other by
86.8°. The Ni–S bond lengths (2.2716(10) and 2.2712(10)
sligthly distorted, with a smaller chelate angle S1–Ni–O2
(81.6°) than that found in complex 4. The Ni–C dis-
tances trans to S are close in both complexes but they are
ꢂ
longer than the Ni-C distance (1.844(8 A) trans to O.
ꢂ
A) are longer that those found in the tetracoordinate
The rotation between the C6F5 rings (88.9°) is similar to
that found in 4, and the angle of the eclipsed cyclo-
pentadienyl rings with the S–P–O chelate plane is 81.1°.
nickel(II) complexes [Ni{S2P(NHiPr)(C6H4OMe)}2]
ꢂ
(2.216(2), 2.225(2), 2.227(2) and 2.228(2) A) [17] and
[Ni{S2P(OEt)(C6H4OMe)}2] (2.2197(8) and 2.2225(8)
ꢂ
The Fe–Ni distance is 5.29 A. The Ni–O bond length is
ꢂ
A) [33] and the hexacoordinate complex [Ni{S2P(OMe)
ꢂ
1.997(4) A and the Ni–S bond length of 2.264(2) A is
ꢂ
ꢂ
(C6H4OMe)}2(py)2] (2.504(1) and 2.494(1) A) [34]. The
ꢂ
P–S distances in 4 (1.997(1) and and 1.991(1) A) are
similar to those found in related compounds indicating
substantial p delocalization of the negative charge over
the S–P–S fragment.
slightly shorter than those observed in complex 4. The
ꢂ
ꢂ
P–O (1.547(5) A) and P–S (1.975(3) A) bond lengths of
the O–P–S fragment are shorter than the corresponding
ꢂ
ones (1.556 and 2.093 A, respectively) found in
[Ti{OSP( ¼ S)(C6H4OMe)}L], L being the tetradentate
ligand 7,16-dihydro-6,8,15,17-tetramethyldibenzo (1,4,
8,11) tetraazacyclotetradecine [35].
3.3. Monothiophosphonate complexes
We have found that the reaction of O-al-
kylferrocenyldithiophosphonic acids, obtained by means
of the ring opening reaction of the 2,4-diferrocenyl-1,3-
dithiadiphosphetane disulfide dimer with alcohols (eth-
anol and 2-propanol), with the hydroxo complex
[NBu4]2[Ni2(C6F5)4(l-OH)2] in dichloromethane at
room temperature (24 h), gives the O-ethyl or O-
isopropyl-ferrocenylmonothiophosphonate nickel com-
plexes 10 and 11 (Scheme 3). The IR spectra of the
complexes show the bands attributed to C6F5 groups
and the corresponding to the thiophosphonate ligands.
4. Supplementary data
Crystallographic data have been deposited with the
Cambridge Crystallographic Data Centre, CCDC No.
196328 (4) and CCDC No.196329 (10), respectively.
Copies of this information may be obtained free of
charge from the Director, CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (fax: +44-(0)1223-336033;
e-mail: deposit@ccdc.cam. ac.uk or www: http://www.
ccdc.cam.ac.uk).
1
The H NMR spectra exhibit the resonance signals of
the aliphatic and ferrocenyl protons, and the 19F NMR
data are consistent with the presence of two different
C6F5 groups, one trans to O and one trans to S.
Acknowledgements
ꢀ
Financial support of this work by the Direccion
General de Investigacion del Ministerio de Ciencia y
ꢀ
Tecnologıa (Project No. BQU2001-0979-C02-01/02),
Spain, is acknowledged.
The crystal structure of 10 (Fig. 2) consists of anionic
mononuclear nickel complexes and tetrabutyl ammo-
nium cations. The planar coordination around nickel is
ꢀ
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