Organometallic nickel(II) complexes containing thiolate and dithiocarbamate ligands

Article abstract of DOI:10.1002/1099-0682(200010)2000:10<2185::AID-EJIC2185>3.0.CO;2-K

The mono(pentafluorophenyl)nickel(II) complexes [Ni(C₆F₅)ClL₂] (L = PPhMe₂, PPh₂Me; L₂ = dppe) react with KSR (R = Ph, C₆H₄Me-p, C₆H₄OMe-p, C₆H₄Cl-p, C₆H₃Cl₂-2,6, C₆H₄NO₂-p) at room temperature in acetone/dichloromethane to give the mononuclear thiolate complexes [Ni(C₆F₅)(SR)L₂]. The binuclear μ-thiolate complex [{Ni(C₆F₅)(PPhMe₂)}₂(μ-SC₆H₄NO₂-p)₂] is obtained by reaction of KSC₆H₄NO₂-p with the same chloro complex in refluxing dichloromethane. A single-crystal X-ray diffraction study of [Ni(C₆F₅)(SC₆H₄NO₂-p)(PPhMe₂)₂] and [{Ni₂(C₆F₅)₂(PPhMe₂)₂(μ-SC₆H₄NO₂-p)₂] has established the mononuclear and binuclear nature of the complexes. The dithiocarbamatenickel complexes [Ni(C₆F₅)(S₂CNR₂)L] (L = PPhMe₂, PPh₂Me, PEt₃; R = Et, iPr; R₂ = C₅H₁₀, C₄H₈O) have been prepared by reaction of [Ni(C₆F₅)ClL₂] (L = PPhMe₂, PPh₂Me, PEt₃) with the alkali metal salt of the corresponding dithioacid. A single-crystal X-ray diffraction study of [Ni(C₆F₅)(S₂CNiP₂)(PPhMe₂)] has established the mononuclear nature of the complex, and the geometry around each Ni atom as that of a tetrahedrally distorted square-planar geometry. Analytical (C, H, N), spectroscopic (IR, ¹H, and ¹⁹F NMR), and mass spectrometry (FAB) data have been used for structural assignments.

Full text of DOI:10.1002/1099-0682(200010)2000:10<2185::AID-EJIC2185>3.0.CO;2-K

FULL PAPER
Organometallic Nickel(II) Complexes Containing Thiolate and
Dithiocarbamate Ligands
[a]
[a]
[b]
[c]
´
´
´
Gregorio Sanchez, Francisco Ruiz, Jose L. Serrano, M. Carmen Ramırez de Arellano,
[a]
´
and Gregorio Lopez*
Keywords: Phosphanes / Nickel / S ligands / Dithiocarbamate complexes / Bioinorganic chemistry
The
mono(pentafluorophenyl)nickel(II)
complexes
thiocarbamatenickel complexes [Ni(C6F5)(S2CNR2)L] (L =
PPhMe2, PPh2Me, PEt3; R = Et, iPr; R2 = C5H10, C4H8O) have
been prepared by reaction of [Ni(C6F5)ClL2] (L = PPhMe2,
PPh2Me, PEt3) with the alkali metal salt of the corresponding
[Ni(C6F5)ClL2] (L = PPhMe2, PPh2Me; L2 = dppe) react with
KSR (R = Ph, C6H4Me-p, C6H4OMe-p, C6H4Cl-p, C6H3Cl2-
2,6, C6H4NO2-p) at room temperature in acetone/dichloro-
methane to give the mononuclear thiolate complexes
[Ni(C6F5)(SR)L2]. The binuclear µ-thiolate complex
dithioacid.
A single-crystal X-ray diffraction study of
[Ni(C6F5)(S2CNiPr2)(PPhMe2)] has established the mononu-
[{Ni(C6F5)(PPhMe2)}2(µ-SC6H4NO2-p)2] is obtained by reac- clear nature of the complex, and the geometry around each
tion of KSC6H4NO2-p with the same chloro complex in re-
fluxing dichloromethane. A single-crystal X-ray diffraction
Ni atom as that of a tetrahedrally distorted square-planar
geometry. Analytical (C, H, N), spectroscopic (IR, 1H, and 19
F
study
of
[Ni(C6F5)(SC6H4NO2-p)(PPhMe2)2]
and
NMR), and mass spectrometry (FAB) data have been used for
structural assignments.
[{Ni2(C6F5)2(PPhMe2)2(µ-SC6H4NO2-p)2] has established the
mononuclear and binuclear nature of the complexes. The di-
Introduction
(L ϭ PPhMe2, PPh2Me) in dichloromethane results in the
rapid formation of the mononuclear arylthiolate complexes
[Ni(C6F5)(SR)L2] (1Ϫ12) shown in Scheme 1. The forma-
Monomeric late transition-metal thiolate complexes have
been receiving increasing attention,[1Ϫ3] in part because of
their relevance as models of biologically redox-active metal-
loproteins.[4] Nickel complexes with S-donor ligands are
present in many hydrogenases.[5] Nickel(II) thiolates are
generally square-planar species with a strong tendency to
form dimers and oligomers.[6Ϫ9] Despite the great amount
of work devoted to the study of metalϪthiolate com-
plexes,[1] fundamental knowledge of the structures of
mononuclear species is relatively sparse.[10,11] Di- and tri-
nuclear pentafluorophenylnickel complexes have been pre-
pared by treating the di-µ-hydroxo-complex [NBu4]2-
[{Ni(C6F5)2(µ-OH)}2] with thiols.[12] Considering related
complexes with S-donor ligands, mononuclear derivatives
such
as
[Ni(C6F5)2(S2CNR2]Ϫ,[13]
[Ni(S2CNEt2)-
(PPh3)2]ϩ,[14] and [Ni(S2COEt)2(PPh3)][15] have also been
studied.
Results and Discussion
Mononuclear Thiolate Complexes
The addition of a methanolic solution of the correspond-
ing alkali metal arylthiolate to a solution of [Ni(C6F5)ClL2]
[a]
´
´
Departamento de Quımica Inorganica, Universidad de Murcia,
E-30071 Murcia, Spain
E-mail: gll@fcu.um.es
[b]
[c]
´
´
´
Departamento de Ingenierıa Minera, Geologica y Cartografica.
´
Universidad Politecnica de Cartagena,
E-30203 Cartagena, Spain
´
´
Departamento de Quımica Organica, Facultad de Farmacia,
Universidad de Valencia,
E-46100 Valencia, Spain
Scheme 1
Eur. J. Inorg. Chem. 2000, 2185Ϫ2191
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
1434Ϫ1948/00/1010Ϫ2185 $ 17.50ϩ.50/0
2185

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G. Sanchez, F. Ruiz, J. L. Serrano, M. C. Ramirez de Arellano, G. Lopez
FULL PAPER
tion of these mononuclear complexes takes place at ambient
temperature; on increasing the temperature, loss of a phos-
phane ligand may occur, and the binuclear µ-arylthiolate
would be the reaction product. In fact, when the solution
containing [Ni(C6F5)Cl(PPhMe2)2] and KSC6H4NO2-4 was
boiled
under
reflux,
the
binuclear
complex
[{Ni(C6F5)(PPhMe2)}2(µ-SC6H4NO2-4)2] (13 in Scheme 1)
was obtained. The trans influence of the pentafluorophenyl
ligand should favour the dissociation of one phosphane mo-
lecule, and the resulting vacant coordination site is occupied
by a µ-arylthiolate group.
The 19F NMR spectra of complexes 1Ϫ13 show the ex-
pected three-resonance signals for a pentafluorophenyl ring
freely rotating around the carbonϪnickel bond
(2 Fo:1 Fp:2 Fm). The experimental NMR pattern consists
of a doublet for the o-fluorine atoms, a triplet for the p-
fluorine atom and multiplet for the m-fluorine atoms. The
observation of a single signal in the 31P NMR spectra indic-
ates that complexes 1Ϫ12 all have the trans geometry shown
in Scheme 1. The same trans geometry should also be as-
signed to complex 13 because only one set of 1H resonances
Figure 1. Molecular structure of compound 12
plex 12 is depicted in Figure 1, and relevant bond lengths
and bond angles are shown in Table 1. The Ni atom and
the four atoms coordinated to it deviate slightly from the
plane defined by them. The NiϪC distance is similar to
values found in other pentafluorophenylnickel com-
pounds;[17,18] the strong trans influence of the C6F5 group
is manifested by a lengthening of the NiϪS bond, giving a
1
for the 4-O2NC6H4S group is found in the H NMR spec-
trum (two doublets for 2,6-H and 3,5-H, respectively, al-
though one doublet is overlapped with the multiplet of the
phenyl group.
In acetone, [Ni(C6F5)Cl(dppe)] reacts with AgClO4 with
elimination of AgCl; on removing the precipitated AgCl,
the addition of an alkali metal thiolate (in methanol) to
the resulting solution gives the corresponding mononuclear
thiolates 14؊19 shown in Scheme 2. The 19F NMR spectra
of these complexes are qualitatively similar to those of
1Ϫ12, but the 31P NMR spectroscopic data indicate the
presence of two nonequivalent phosphorus atoms, one trans
to S and one trans to C, and two 31P resonances are found
in the range δ ϭ 50Ϫ56; the multiplet structure of the low-
field signal is due to coupling to the o-fluorine atoms of
the pentafluorophenyl group and this signal is consequently
assigned to the phosphorus atom trans to C6F5.
˚
distance of 2.233 A, which is significantly longer than those
found in homoleptic nickel-thiolate complexes.[19]
The structure of complex 13 consists of centrosymmetric
binuclear molecules with two Ni atoms bridged by arylthi-
olate groups (Figure 2). Bond lengths and bond angles are
given in Table 1. The nickel atoms have approximately
square-planar coordination, the deviation from the ideal
geometry being revealed by the SϪNiϪS angles. The NiϪS
distances, 2.2140(11) and 2.2490(11), are quite similar to
those found in the asymmetric binuclear complex
[(C6F5)2Ni(µ-SPh)2Pd(dppe)] [2.214(2) and 2.2509(14)].[20]
In the trinuclear complex [Ni3(C6F5)4(µ-SEt)4] a weighted
mean NiϪS distance of 2.203(5) was observed.[12]
Dithiocarbamate Complexes
The addition of a methanolic solution of the alkali metal
dithiocarbamate (diethyldithiocarbamate, diisopropyldithio-
carbamate, piperidinecarbodithioate, and morpholinecar-
bodithioate) to a solution of [Ni(C6F5)ClL2] (L ϭ PPhMe2,
PPh2Me, PEt3) in dichloromethane results in the formation
of the dithiocarbamate complexes [Ni(C6F5)(S2CNR2)L]
(20Ϫ31) with loss of one phosphane molecule (Scheme 3).
The 19F NMR spectra of the dithiocarbamatenickel com-
plexes exhibit the three signals (2 Fo:1 Fp:2 Fm) correspond-
ing to a freely rotating C6F5 ring, and the 31P NMR spectra
show the single resonance expected for the phosphane li-
gand. The most relevant IR absorptions of coordinated di-
Scheme 2
The neutral compounds 1؊19 show the characteristic
infrared absorptions of the pentafluorophenyl group[16] at
ca. 1630m, 1495vs, 1050s, 950vs, and 780s cmϪ1
.
Crystal Structures of Complexes 12 and 13
The X-ray crystal structure determinations carried out thiocarbamate are those originating from the thioureide
for complexes [Ni(C6F5)(SC6H4NO2-4)(PPhMe2)2] (12) and group. In complexes 20Ϫ31, the CϪN and CϪS stretching
[{Ni(C6F5)(PPhMe2)}2(µ-SC6H4NO2-4)2] (13) show the vibrations[21,22,23] are found at 1550Ϫ1450 cmϪ1 and
mono- and di-nuclearity of these complexes. A view of com- 995Ϫ970 cmϪ1, respectively, and the presence of only one
2186
Eur. J. Inorg. Chem. 2000, 2185Ϫ2191

Organometallic Nickel(II) Complexes Containing Thiolate and Dithiocarbamate Ligands
FULL PAPER
˚
Table 1. Selected bond lengths [A] and angles [°] for complexes 12, 13, and 24
12
13
24
Bond lengths
NiϪC(11)
1.911(2)
NiϪC(1)
NiϪS
1.899(4)
NiϪC(1)
NiϪS(1)
NiϪS(2)
NiϪP
1.923(2)
NiϪP(1)
2.2087(7)
2.1905(7)
2.2335(7)
2.2140(11)
2.1807(12)
2.2490(11)
2.2029(5)
2.2144(5)
2.1683(5)
NiϪP(2)
NiϪS
NiϪP
NiϪS#1
Bond angles
C(11)ϪNiϪP(1)
C(11)ϪNiϪP(2)
P(1)ϪNiϪS
P(2)ϪNiϪS
89.98(7)
91.63(7)
89.01(2)
89.42(3)
C(1)ϪNiϪP
PϪNiϪS
C(1)ϪNiϪS#1
SϪNiϪS#1
88.17(14)
97.73(4)
90.53(14)
83.72(4)
C(1)ϪNiϪP
C(1)ϪNiϪS(1)
PϪNiϪS(2)
91.80(5)
91.40(5)
98.11(2)
78.77(2)
S(1)ϪNiϪS(2)
Figure 3. Molecular structure of compound 24
Figure 2. Molecular structure of compound 13
gram is provided in Figure 3, and relevant bond lengths and
angles are reported in Table 1. The overall coordination
geometry about the nickel atom is essentially square planar.
The S1ϪNiϪS2 angle is restricted by the chelate ring to
78.77(2)°. The PϪNiϪS2 bond angle compensates to a
great extent for the low angle by opening to 98.11(2)° with
the C1ϪNiϪS1 angle at 91.40(5)°. The strong NiϪC6F5
bonding is evident in the nonequivalent NiϪS1 and NiϪS2
bond lengths and the trans influence exerted by the pen-
tafluorophenyl ring is higher than that of the phosphane
ligand lengthening the bond NiϪS2 giving a distance of
Scheme 3
˚
2.2144(5) A, longer than the distance NiϪS1, 2.2029(5).
band for ν(CS) is consistent with bidentate coordination of
the dithiocarbamate.[24,25] Since the CϭN and CϪN
stretching vibrations are usually found at 1690Ϫ1640 and
Conclusion
1350Ϫ1250 cmϪ1 [25]
the thioureide band at 1550Ϫ1450
,
This work shows that mononuclear Ni-thiolate com-
plexes [Ni(C6F5)(SR)L2] can be conveniently prepared by
metathetical reactions carried out with the corresponding
chloro complexes [Ni(C6F5)ClL2]. The reaction temperature
is a decisive factor in the formation of the mononuclear
thiolate complex. At room temperature the mononuclear
thiolato complex is the outcome of the metathetical reac-
tion, but if the reaction is carried out in refluxing dichloro-
cmϪ1 indicates that the CϪN bond in the coordinated
(S2CNR2)Ϫ has considerable double bond character. How-
ever, the 1H NMR spectra of complexes 20Ϫ31 indicate that
rotation of the NR2 group around the CϪN bond is not
hindered.
Crystal Structure of Complex 24
The structure of [Ni(C6F5)(S2CNiPr2)(PPhMe2)] (24) has methane the binuclear thiolate complex is obtained with the
been determined by X-ray crystallography. An ORTEP dia- concomitant release of one L molecule. The dithiocarba-
Eur. J. Inorg. Chem. 2000, 2185Ϫ2191
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FULL PAPER
5: Yield 74%. Ϫ C38H29Cl2F5NiP2S (804.3): calcd. C 56.7, H 3.6,
S 4.0; found C 56.5, H 3.8, S 4.1. Ϫ M.p. 160 °C (dec.). Ϫ 1H
NMR ([D6]acetone): δ ϭ 1.7 (t, 6 H, PPh2Me), 6.5 (t, 1 H,
SC6H4Cl2Ϫ2,6), 6.9 (d, 2 H, SC6H4Cl2-2,6), 7.4 (m, 12 H, PPh2Me),
8.0 (m, 8 H, PPh2Me). Ϫ 19F NMR ([D6]acetone): δ ϭ Ϫ113.6 (d,
Jom ϭ 26.9 Hz, 2 Fo), Ϫ162.3 (t, Jmp ϭ 20.8 Hz, 1 Fp), Ϫ163.8 (m,
2 Fm). Ϫ 31P{1H} NMR ([D6]acetone): δ ϭ 4.0 (s).
mate complexes are similarly obtained when [Ni(C6F5)ClL2]
is treated with KS2CNR2.
Experimental Section
General Methods: C, H, and N analyses were carried out with a
Carlo Erba instrument. Ϫ Infrared spectra were recorded with a
PerkinϪElmer 16F-PC-FT spectrophotometer using Nujol mulls
between polyethylene sheets. Ϫ 1H, 31P, and 19F NMR spectra were
recorded with a Bruker AC 200E or a Varian 300 spectrometer.
Ϫ Conductance measurements were performed with a Crison 525
conductimeter (in acetone solution, c ഠ 5 ϫ 10Ϫ4 mol·dmϪ3). Ϫ
Decomposition temperatures were determined with a Reichert mi-
croscope. Ϫ All solvents were dried by conventional methods. Ϫ
6: Yield 76%. Ϫ C38H30F5NNiO2P2S (780.4): calcd. C 58.5, H 3.9,
N 1.8, S 4.1; found C 58.7, H 4.1, N 1.9, S 4.3. Ϫ M.p. 170 °C
(dec.). Ϫ 1H NMR ([D6]acetone): δ ϭ 1.6 (t, 6 H, PPh2Me), 7.3
(m, 12 H, PPh2Me), 7.5 (m, 8 H, PPh2Me, SC6H4NO2-p), 7.6 (d, 2
H, SC6H4Cl-p). Ϫ 19F NMR ([D6]acetone): δ ϭ Ϫ117.2 (d, Jom
ϭ
23.5 Hz, 2 Fo), Ϫ160.9 (t, Jmp ϭ 19.7 Hz, 1 Fp), Ϫ162.6 (m, 2 Fm).
Ϫ
31P{1H} NMR ([D6]acetone): δ ϭ 7.6(s).
7: Yield 79%. Ϫ C28H27F5NiP2S (611.2): calcd. C 55.0, H 4.5, S
The
compounds
[Ni(C6F5)Cl(PPhMe2)2],[18]
[Ni(C6F5)Cl-
1
5.2; found C 55.2, H 4.8, S 5.3. Ϫ M.p. 120 °C (dec.). Ϫ H NMR
(PPh2Me)2],[19] [Ni(C6F5)Cl(dppe)],[26] and [Ni(C6F5)Cl(PEt2)2][19]
were prepared as described elsewhere.
([D6]acetone)]: δ ϭ 1.3 (t, 12 H, PPhMe2), 7.0 (m, 3 H, SPh), 7.3
(m, 10 H, PPhMe2), 7.8 (d, 2 H, SPh). Ϫ 19F NMR ([D6]acetone):
δ ϭ Ϫ117.6 (d, Jom ϭ 27.0 Hz, 2 Fo), Ϫ161.1 (t, Jmp ϭ 19.7 Hz,
1 Fp), Ϫ163.3 (m, 2 Fm). Ϫ 31P{1H} NMR ([D6]acetone): δ ϭ Ϫ3.7.
[Ni(C6F5)(SR)L2]; L ؍ PPh2Me and R ؍ Ph (1), C6H4Me-p (2),
C6H4OMe-p (3), C6H4Cl-p (4), C6H4Cl2؊2,6 (5), C6H4NO2-p (6);
L ؍ PPhMe2 and R ؍ Ph (7), C6H4Me-p (8), C6H4OMe-p (9),
C6H4Cl-p (10), C6H4Cl2-2,6 (11), C6H4NO2-p (12): A solution of
[Ni(C6F5)ClL2] ( 0.164 mmol) in dichloromethane (10 mL) was ad-
ded to a solution of KSR (0.164 mmol) in methanol (10 mL), and
the solution was stirred at room temperature for 30 min. It was
concentrated under reduced pressure to ca. 5 mL. The addition of
water (ca. 1 mL) caused precipitation of a red solid, which was
filtered off, washed with hexane and air-dried. The complexes were
recrystallized from dichloromethane/hexane.
8: Yield 71%. Ϫ C29H29F5NiP2S (625.3): calcd. C 55.7, H 4.7, S
1
5.1; found C 55.5, H 4.8, S 5.4. Ϫ M.p. 130 °C (dec.). Ϫ H NMR
([D6]acetone): δ ϭ 1.3 (t, 12 H, PPhMe2), 2.2 (s, 3 H, Me), 6.8 (d,
2 H, SC6H4Me-p), 7.2 (m, 10 H, PPhMe2), 7.7 (d, 2 H, SC6H4Me-
p). Ϫ 19F NMR ([D6]acetone): δ ϭ Ϫ116.6 (d, Jom ϭ 26.6 Hz, 2 Fo),
Ϫ162.5 (t, Jmp ϭ 20.0 Hz, 1 Fp), Ϫ163.8 (m, 2 Fm). Ϫ 31P{1H}
NMR ([D6]acetone): δ ϭ Ϫ3.6 (s).
9: Yield 75%. Ϫ C29H29F5NiOP2S (641.2): calcd. C 54.3, H 4.6, S
1
5.0; found C 54.6, H 4.9, S 4.9. Ϫ M.p. 135 °C (dec.). Ϫ H NMR
([D6]acetone): δ ϭ 1.3 (t, 12 H, PPhMe2), 3,7 (s, 3 H, MeO), 6.6
(d, 2 H, SC6H4MeO-p), 7.2 (m, 10 H, PPhMe2), 7.7 (d, 2 H,
1: Yield: 72%. Ϫ C38H31F5NiP2S (735.4): calcd. C 62.1, H 4.2, S
4.4; found C 62.0, H 4.4, S 4.2. Ϫ M.p. 156 °C (dec.). Ϫ H NMR
1
SC6H4MeO-p). Ϫ 19F NMR ([D6]acetone): δ ϭ Ϫ117.5 (d, Jom
ϭ
([D6]acetone): δ ϭ 1.7 (t, 6 H, PPh2Me), 7.0 (m, 3 H, SPh), 7.2 (m,
12 H, PPh 2Me), 7.5 (m, 8 H, PPh2Me), 7.7 (d, 2 H, SPh). Ϫ 19F
NMR ([D6]acetone): δ ϭ Ϫ116.7 (d, Jom ϭ 25.0 Hz, 2 Fo), Ϫ162.3
(t, Jmp ϭ 19.8 Hz, 1 Fp), Ϫ163.7 (m, 2 Fm). Ϫ 31P{1H} NMR
([D6]acetone): δ ϭ 8.4 (s).
27.9 Hz, 2 Fo), Ϫ161.1 (t, Jmp ϭ 20.0 Hz, 1 Fp), Ϫ163.3 (m, 2 Fm).
Ϫ
31P{1H} NMR ([D6]acetone): δ ϭ Ϫ3.7 (s).
10: Yield 81%. Ϫ C28H26ClF5NiP2S (645.7): calcd. C 52.1, H 4.1,
S 5.0; found C 52.4, H 4.0, S 4.8. Ϫ M.p. 130 °C (dec.). Ϫ 1H NMR
([D6]acetone): δ ϭ 1.3 (t, 12 H, PPhMe2), 6.9 (d, 2 H, SC6H4Cl-p),
7.2 (m, 10 H, PPhMe2), 7.7 (d, 2 H, SC6H4Cl-p). Ϫ 19F NMR
([D6]acetone): δ ϭ Ϫ117.7 (d, Jom ϭ 24.8 Hz, 2 Fo), Ϫ160.7 (t,
2: Yield: 70%. Ϫ C39H33F5NiP2S (749.4): calcd. C 62.5, H 4.4, S
1
4.3; found C 62.2, H 4.5, S 4.6. Ϫ M.p. 160 °C (dec.). Ϫ H NMR
([D6]acetone): δ ϭ 1.7 (t, 6 H, PPh2Me), 2.2 (s, 3 H, SC6H4Me-p),
6.8 (d, 2 H, SC6H4Me-p), 7.2 (m, 12 H, PPh2Me), 7.5 (m, 8 H,
PPh2Me), 7.7 (d, 2 H, SC6H4Me-p). Ϫ 19F NMR ([D6]acetone):
δ ϭ Ϫ116.6 (d, Jom ϭ 24.6 Hz, 2 Fo), Ϫ162.5 (t, Jmp ϭ 20.0 Hz,
1 Fp), Ϫ163.8 (m, 2 Fm). Ϫ 31P{1H} NMR ([D6]acetone): δ ϭ 8.3
(s).
J
mp ϭ 19.8 Hz, 1 Fp), Ϫ163.0 (m, 2 Fm). Ϫ 31P{1H} NMR ([D6]ace-
tone): δ ϭ Ϫ3.8.
11: Yield 80%. Ϫ C28H25Cl2F5NiP2S (680.1): calcd. C 49.4, H 3.7,
S 4.7; found C 49.6, H 3.9, S 4.9. Ϫ M.p. 155 °C (dec.). Ϫ 1H
NMR ([D6]acetone): δ ϭ 1.3 (t, 12 H, PPhMe2), 6.7 (t, 1 H,
SC6H4Cl2-2,6), 7.1 (d, 2 H, SC6H4Cl2-2,6), 7.2 (m, 10 H, PPhMe2).
3: Yield 76%. Ϫ C39H33F5NiOP2S (765.4): calcd. C 61.2, H 4.3, S
Ϫ
19F NMR ([D6]acetone): δ ϭ Ϫ115.9 (d, Jom ϭ 26.9 Hz, 2 Fo),
1
4.2; found C 61.0, H 4.6, S 4.5. Ϫ M.p. 155 °C (dec.). Ϫ H NMR
Ϫ161.5 (t, Jmp ϭ 20.8 Hz, 1 Fp), Ϫ163.5 (m, 2 Fm). Ϫ 31P{1H}
NMR ([D6]acetone): δ ϭ Ϫ5.8.
([D6]acetone): δ ϭ 1.7 (t, 6 H, PPh2Me), 3.7 (s, 3 H, SC6H4MeO-
p), 6.5 (d, 2 H, SC6H4MeO-p), 7.4 (m, 14 H, PPh2Me), 7.5 (m, 6
H, PPh2Me), 7.6 (d, 2 H, SC6H4MeO-p). Ϫ 19F NMR ([D6]ace-
12: Yield 83%. Ϫ C28H26F5NNiO2P2S (656.2): calcd. C 51.2, H 4.0,
N 2.1, S 4.9; found C 51.0, H 4.1, N 2.0, S 4.7. Ϫ M.p. 160 °C
tone): δ ϭ Ϫ116.6 (d, Jom ϭ 22.9 Hz, 2 Fo), Ϫ162.5 (t, Jmp
ϭ
21.4 Hz, 1 Fp), Ϫ163.8 (m, 2 Fm). Ϫ 31P{1H} NMR ([D6]acetone):
δ ϭ 8.3 (s).
1
(dec.). Ϫ H NMR ([D6]acetone): δ ϭ 1.3 (t, 12 H, PPhMe2), 7.2
(m, 12 H, PPhMe2 ϩ SC6H4NO2-p), 7.7 (d, 2 H, SC6H4NO2-p). Ϫ
19F NMR ([D6]acetone): δ ϭ Ϫ117.2 (d, J
ϭ 23.5 Hz, 2 Fo),
om
4: Yield 77%. Ϫ C38H30ClF5NiP2S (769.8): calcd. C 59.3, H 3.9, S
Ϫ160.9 (t, Jmp ϭ 19.7 Hz, 1 Fp), Ϫ162.6 (m, 2 Fm). Ϫ 31P{1H}
1
4.2; found C 59.5, H 4.2, S 4.4. Ϫ M.p. 150 °C (dec.). Ϫ H NMR
NMR ([D6]acetone): δ ϭ Ϫ3.8.
([D6]acetone): δ ϭ 1.7 (t, 6 H, PPh2Me), 6.8 (d, 2 H, SC6H4Cl-p),
7.2 (m, 14 H, PPh2Me), 7.4 (m, 6 H, PPh2Me), 7.6 (d, 2 H, [{Ni(C6F5)(PPhMe2)}2(µ-SC6H4NO2-p)2] (13):
SC6H4Cl-p). Ϫ 19F NMR ([D6]acetone): δ ϭ Ϫ116.6 (d, Jom
[Ni(C6F5)Cl(PPhMe2)2] (0.164 mmol) in dichloromethane (10 mL)
24.8 Hz, 2 Fo), Ϫ161.8 (t, Jmp ϭ 19.8 Hz, 1 Fp), Ϫ163.4 (m, 2 Fm). was added to a solution of KSC6H4NO2-p (0.164 mmol) in meth-
A
solution of
ϭ
Ϫ
31P{1H} NMR ([D6]acetone): δ ϭ 8.0 (s).
anol (10 mL), and the solution was heated under reflux for 5 h.
2188
Eur. J. Inorg. Chem. 2000, 2185Ϫ2191

Organometallic Nickel(II) Complexes Containing Thiolate and Dithiocarbamate Ligands
FULL PAPER
The solvent was then partly evaporated under reduced pressure to
half the original volume, and the addition of diethyl ether caused
19: Yield 86%. Ϫ C38H28F5NNiO2P2S (778.3): calcd. C 58.6, H 3.6,
N 1.8, S, 4.1; found C 58.8, H 3.5, N 2.0, S 4.2. Ϫ M.p. 200 °C
1
the precipitation of a red-brown solid, which was filtered off, (dec.). Ϫ H NMR ([D6]acetone): δ ϭ 2.2 (m, 4 H, dppe), 7.2 (d,
washed with hexane and air-dried. The complex was recrystallized
from dichloromethane/diethyl ether. Yield: 83%.
2 H, SC6H4NO2-p), 7.4 (m, 4 H, dppe), 7.6 (m, 12 H, dppe), 7.9
(m, 4 H, dppe), 8.2 (d, 2 H, SC6H4NO2-p). Ϫ 19F NMR ([D6]ace-
tone): δ ϭ Ϫ116.7 (m, 2 Fo), Ϫ162.1 (t, Jmp ϭ 21.4 Hz, 1 Fp),
Ϫ164.2 (m, 2 Fm). Ϫ 31P{1H} NMR ([D6]acetone): δ ϭ 51.2 (d,
Ϫ
Ϫ
C40H30F10N2Ni2O4P2S2 (1036): calcd. C 46.4, H 2.9, N 2.7, S 6.2;
found C 46.1, H 3.1, N 2.6, S 6.5. Ϫ M.p. 165 °C (dec.). Ϫ 1H
NMR ([D6]acetone): δ ϭ 1.3 (t, 12 H, PPhMe2), 7.3 (m, 14 H, 2J ϭ 42.7 Hz, PA), 56.0 (d, PB).
PPhMe2 ϩ SC6H4NO2-p), 7.8 (d, 4 H, SC6H4NO2-p). Ϫ 19F NMR
[Ni(C6F5)(S2CNR2)L]; R ؍ Et and L ؍ PPh2Me (20), PPhMe2
(21), PEt3 (22); R ؍ iPr and L ؍ PPh2Me (23), PPhMe2 (24), PEt3
(25); R ؍ C5H10 and L ؍ PPh2Me (26), PPhMe2 (27), PEt3 (28);
R ؍ C4H8 and L ؍ PPh2Me (29), PPhMe2 (30), PEt3 (31): Potas-
sium dialkyldithiocarbamate (0.164 mmol) was added to a solution
of [Ni(C6F5)ClL2] (0.164 mmol) in acetone (20 mL) and the solu-
tion was stirred at room temperature for 15 min. It was concen-
trated under reduced pressure to ca. 5 mL. The addition of water
(1 mL) caused precipitation of an orange solid, which was filtered
off, washed with hexane and air-dried. The complexes were recrys-
tallized from dichloromethane/hexane.
([D6]acetone): δ ϭ Ϫ116.2 (d, Jom ϭ 30.2, 2 Fo), Ϫ160.2 (t, Jmp
ϭ
19.7, 1 Fp), Ϫ162.4 (m, 2 Fm). Ϫ 31P{1H} NMR ([D6]acetone): δ ϭ
Ϫ 5.0.
[Ni(C6F5)(SR)(dppe)]; R ؍ Ph (14), C6H4Me-p (15), C6H4OMe-p
(16), C6H4Cl-p (17), C6H4Cl2؊2,6 (18), C6H4NO2-p (19): AgClO4
(0.157 mmol) was added to a solution of [Ni(C6F5)Cl(dppe)]
(100 mg, 0.157 mmol) in acetone (20 mL). After stirring at room
temperature for 1 h, the precipitated AgCl was filtered off and the
resulting solution was added to a solution of KSR (0.157 mmol) in
methanol (10 mL). The solution was then stirred at room temper-
ature for 30 min. It was concentrated under reduced pressure to ca.
5 mL. The addition of water (ca. 1 mL) caused precipitation of a
brown solid, which was filtered off, washed with hexane and air-
dried. The complexes were recrystallized from dichloromethane/
hexane.
20: Yield 82%. Ϫ C24H23F5NNiPS2 (574.2): calcd. C 50.2, H 4.0,
N 2.4, S 11.2; found C 50.3, H 3.8, N 2.5, S 11.5. Ϫ M.p. 124 °C
1
(dec.). Ϫ H NMR ([D6]acetone): δ ϭ 1.2 (t, 6 H, Et), 1.4 (t, 3 H,
PPh2Me), 3.6 (m, 4 H, Et), 7.4 (m, 6 H, PPh2Me), 7.6 (m, 4 H,
PPh2Me). Ϫ 19F NMR ([D6]acetone): δ ϭ Ϫ116.7 (d, 2 Fo, Jom
ϭ
14: Yield 77%. Ϫ M.p. 215 °C (dec.). Ϫ C38H29F5NiP2S (733.3): C
62.2, H 4.0, S 4.4; found C 62.0, H 4.2, S 4.6. Ϫ 1H NMR ([D6]ace-
tone): δ ϭ 2.1 (m, 4 H, dppe), 6.6 (m, 3 H, SPh), 7.1 (d, 2 H, SPh),
7.4 (m, 16 H, dppe), 8.0 (m, 4 H, dppe). Ϫ 19F NMR ([D6]acetone):
δ ϭ Ϫ116.9 (m, 2 Fo), Ϫ164.1 (t, Jmp ϭ 21.4, 1 Fp), Ϫ165.2 (m,
2 Fm). 31P{1H} NMR ([D6]acetone): δ ϭ 50.4 (m, PA), 54.8 (d, 2J ϭ
40.4, PB).
23.7), Ϫ161.8 (t, Jm,p ϭ 19.7 Hz, 1 Fp), Ϫ164.3 (m, 2 Fm). Ϫ
31P{1H} NMR ([D6]acetone): δ ϭ 15.4 (s).
21: Yield 79%. Ϫ C19H21F5NNiPS2 (512.7): calcd. C 44.6, H 4.1,
N 2.7, S 12.5; found C 44.3, H 3.9, N 2.6, S 12.4. Ϫ M.p. 119 °C
(dec.). Ϫ 1H NMR ([D6]acetone): δ ϭ 1.2 (t, 6 H, Et), 1.4 (m, 6
H, PPhMe2), 3.6 (m, 4 H, Et), 7.4 (m, 3 H, PPh2Me), 7.6 (m, 2 H,
PPh2Me). Ϫ 19F NMR ([D6]acetone): δ ϭ Ϫ117.1 (d, Jom
ϭ
15: Yield 81%. Ϫ C39H31F5NiP2S (747.4): calcd. C 62.7, H 4.2, S
25.8 Hz, 2 Fo), Ϫ161.5 (t, Jmp ϭ 19.2 Hz, 1 Fp), Ϫ164.3 (m, 2 Fm).
1
Ϫ
31P{1H} NMR ([D6]acetone): δ ϭ 1.4 (s).
4.3; found C 62.4, H 4.3, S 4.5. Ϫ M.p. 195 °C (dec.). Ϫ H NMR
([D6]acetone): δ ϭ 2.1 (s, 3 H, SC6H4Me-p), 2.5 (m, 4 H, dppe),
6.3 (d, 2 H, SC6H4Me-p), 6.8 (d, 2 H, SC6H4Me-p), 7.4 (m, 20 H,
dppe). Ϫ 19F NMR ([D6]acetone): δ ϭ Ϫ116.9 (m, 2 Fo), Ϫ164.7
(t, Jmp ϭ 21.4 Hz, 1 Fp), Ϫ165.4 (m, 2 Fm). Ϫ 31P{1H} NMR
22: Yield 72%. Ϫ C17H25F5NNiPS2 (492.2): calcd. C 41.5, H 5.1,
N 2.8, S 13.0; found C 41.2, H 5.0, N 2.8, S 13.1. Ϫ M.p. 112 °C
1
(dec.). Ϫ H NMR ([D6]acetone): δ ϭ 1.2 (m, 15 H, Et ϩ PEt3),
1.3 (m, 6 H, PEt3), 3.6 (q, 4 H, Et). Ϫ 19F NMR ([D6]acetone):
δ ϭ Ϫ116.3 (d, Jom ϭ 25.0, 2 Fo), Ϫ161.7 (t, J mp ϭ 19.7 Hz, 1 Fp),
Ϫ164.2 (m, 2 Fm). Ϫ 31P{1H} NMR ([D6]acetone): δ ϭ 21.0 (s).
2
([D6]acetone): δ ϭ 50.5 (m, PA), 54.5 (d, J ϭ 40.4 Hz, PB).
16: Yield 82%. Ϫ C39H31F5NiOP2S (763.4): calcd. C 61.4, H 4.1, S
1
4.2; found C 61.5, H 4.4, S 4.3. Ϫ M.p. 198 °C (dec.). Ϫ H NMR
23: Yield 71%. Ϫ C26H27F5NNiPS2 (602.3): calcd. C 51.9, H 4.5,
N 2.3, S 10.6; found C 51.6, H 4.4, N 2.4, S 10.4. Ϫ M.p. 151 °C
(dec.). Ϫ 1H NMR ([D6]acetone): δ ϭ 1.4 (m, 15 H, iPr ϩ
PPh2Me), 4.5 (m, 2 H, iPr), 7.4 (m, 6 H, PPh2Me), 7.6 (m, 4 H,
([D6]acetone): δ ϭ 2.1 (m, 4 H, dppe), 3.6 (s, 3 H, SC6H4MeO-p),
6.3 (d, 2 H, SC6H4MeO-p), 7.0 (d, 2 H, SC6H4MeO-p), 7.4 (m, 16
H, dppe), 8.0 (m, 4 H, dppe). Ϫ 19F NMR ([D6]acetone): δ ϭ
Ϫ116.9 (m, 2 Fo), Ϫ164.3 (t, Jmp ϭ 21.4 Hz, 1 Fp), Ϫ165.0 (m,
2 Fm). Ϫ 31P{1H} NMR ([D6]acetone): δ ϭ 50.4 (m, PA), 54.3 (d,
2J ϭ 40.4 Hz, PB).
PPh2Me). Ϫ 19F NMR ([D6]acetone): δ ϭ Ϫ116.4 (d, Jom
ϭ
23.4 Hz, 2 Fo), Ϫ162.1 (t, Jmp ϭ 19.7 Hz, 1 Fp), Ϫ164.4 (m, 2 Fm).
Ϫ
31P{1H} NMR ([D6]acetone): δ ϭ 15.3 (s).
17: Yield 84%. Ϫ C38H28ClF5NiP2S (767.8): calcd. C 59.5, H 3.7,
S 4.2; found C 59.8, H 4.0, S 4.3. Ϫ M.p. 190 °C (dec.). Ϫ 1H
NMR ([D6]acetone): δ ϭ 2.1 (m, 4 H, dppe), 6.7 (d, 2 H, SC6H4Cl-
p), 7.0 (d, 2 H, SC6H4Cl-p), 7.5 (m, 16 H, dppe), 8.0 (m, 4 H,
dppe). Ϫ 19F NMR ([D6]acetone): δ ϭ Ϫ116.8 (m, 2 Fo), Ϫ163.2
24: Yield 78%. Ϫ C21H25F5NNiPS2 (540.2): calcd. C 46.7, H 4.6,
N 2.6, S 11.9; found C 46.6, H 4.5, N 2.5, S 11.7. Ϫ M.p. 136 °C
(dec.). Ϫ 1H NMR ([D6]acetone): δ ϭ 1.4 (m, 18 H, iPr ϩ
PPhMe2), 4.5 (m, 2 H, iPr), 7.4 (m, 3 H, PPhMe2), 7.6 (m, 2 H,
PPh2Me). Ϫ 19F NMR ([D6]acetone): δ ϭ Ϫ116.7 (d, Jom ϭ 24.0,
2 Fo), Ϫ161.6 (t, Jmp ϭ 19.5 Hz, 1 Fp), Ϫ164.2 (m, 2 Fm). Ϫ
31P{1H} NMR ([D6]acetone): δ ϭ 1.3 (s).
(t, J
ϭ 21.4 Hz, 1 Fp), Ϫ164.8 (m, 2 Fm). Ϫ 31P{1H} NMR
mp
2
([D6]acetone): δ ϭ 52.1 (m, PA), 56.1 (d, J ϭ 41.4 Hz, PB).
18: Yield 80%. Ϫ C38H27Cl2F5NiP2S (802.2): calcd. C 56.9, H 3.4,
S 4.0; found C 57.0, H 3.2, S 4.2. Ϫ M.p. 205 °C (dec.). Ϫ 1H
NMR ([D6]acetone): δ ϭ 2.2 (m, 4 H, dppe), 6.6 (t, 1 H, SC6H3Cl2-
2,6), 6.9 (d, 2 H, SC6H3Cl2-2,6), 7.4 (m, 16 H, dppe), 8.0 (m, 4 H,
25: Yield 75%. Ϫ C19H29F5NNiPS2 (520.4): calcd. C 43.9, H 5.6,
N 2.7, S 12.3; found C 44.0, H 5.6, N 2.6, S 12.2. Ϫ M.p. 115 °C
1
(dec.). Ϫ H NMR ([D6]acetone): δ ϭ 1.4 (m, 27 H, iPr ϩ PEt3),
dppe). Ϫ 19F NMR ([D6]acetone): δ ϭ Ϫ114.2 (m, 2 Fo), Ϫ163.8 4.5 (m, 2 H, iPr). Ϫ 19F NMR ([D6]acetone): δ ϭ Ϫ116.2 (d, Jom ϭ
(t, Jmp ϭ 19.8 Hz, 1 Fp), Ϫ164.5 (m, 2 Fm). Ϫ 31P{1H} NMR 25.0 Hz, 2 Fo), Ϫ161.9 (t, Jmp ϭ 19.8 Hz, 1 Fp), Ϫ164.3 (m, 2 Fm).
([D6]acetone): δ ϭ 52.0 (m, PA), 54.6 (m, PB).
Ϫ
31P{1H} NMR ([D6]acetone): δ ϭ 20.3 (s).
Eur. J. Inorg. Chem. 2000, 2185Ϫ2191
2189

´
´
G. Sanchez, F. Ruiz, J. L. Serrano, M. C. Ramirez de Arellano, G. Lopez
FULL PAPER
Table 2. Crystal data and parameter of data collection for complexes 12, 13, and 24
12
13
24
Empirical formula
Formula mass
C28H26F5NNiO2P2S
656.21
C40H30F10N2Ni2O4P2S2
1036.14
C21H25F5NNiPS2
540.22
Temperature
293(2) K
173(2) K
173(2) K
Absorption coefficient
Crystal system
9.30 cmϪ1
monoclinic
P21/c
12.18 cmϪ1
monoclinic
P21/c
11.08 cmϪ1
monoclinic
Space group
P21/c
˚
˚
˚
Unit cell dimensions
a ϭ 15.647(4) A
a ϭ 10.2451(14) A
a ϭ 14.6464(12)
b ϭ 11.9076(10)
c ϭ 13.8742(12)
β ϭ 101.086(6) °
˚
b ϭ 10.4481(14) A
b ϭ 8.38.01(10) A
˚
˚
c ϭ 19.035(3) A
c ϭ 23.523(3) A
β ϭ 114.21(2)°
β ϭ 97.681(10)°
3
3
3
3
˚
˚
˚
˚
Z; V A
4; 2838.3(9) A
2; 2001.5(5) A
4; 2374.6(3) A
Density (calculated)
Wavelength (Mo-Kα)
F (000)
1.361 g·cmϪ3
1.719 g·cmϪ3
1.511 g·cmϪ3
˚
˚
˚
0.71073 A
0.71073 A
0.71073 A
1344
1048
1112
Independent reflections
Parameters
R1
4937
3514
4183
365
248
286
0.0429
0.1011
0.0653
0.1162
0.0283
0.0591
wR2
26: Yield 77%. Ϫ C25H23F5NNiPS2 (586.26): calcd. C 51.2, H 3.9,
N 2.4, S 10.9; found C 51.1, H 4.0, N 2.4, S 10.6. Ϫ M.p. 170 °C
Determination of the X-ray Crystal Structures of 12, 13, and 24:
Single crystals of complexes 12 (approximate dimensions 0.75 ϫ
0.50 ϫ 0.40 mm), 13 (0.50 ϫ 0.30 ϫ 0.20 mm), and 24 (0.60 ϫ 0.50
ϫ 0.30 mm) were mounted on a Siemens P4 diffractometer with
(dec.). Ϫ 1H NMR ([D6]acetone): δ ϭ 1.6 (m, 9 H, C5H10
ϩ
PPh2Me), 3.7 (m, 4 H, C5H10), 7.4 (m, 6 H, PPh2Me), 7.6 (m, 4 H,
PPh2Me). Ϫ 19F NMR ([D6]acetone): δ ϭ Ϫ116.7 (d, Jom ϭ 24.0, LT2 temperature attachment. The crystallographic data are shown
˚
2 Fo), Ϫ161.8 (t, Jmp ϭ 19.8 Hz, 1 Fp), Ϫ164.3 (m, 2 Fm). Ϫ
in Table 2. The scan method was ω with 2Θmax ϭ 50 for the three
31P{1H} NMR ([D6]acetone): δ ϭ 15.6 (s).
cases, empirical Ψ-scan mode absorption was made. The structures
were solved by direct methods and refined anisotropically on F2.[26]
The final R factors were 0.0367, 0.0451 and 0.0233 in 12, 13, and
24, respectively {Rw ϭ 0.0986, 0.1091, and 0.058, w ϭ 1/[σ2 (F2) ϩ
27: Yield 76%. Ϫ C20H21F5NNiPS2 (524.2): calcd. C 45.8, H 4.0,
N 2.7, S 11.2; found C 45.6, H 4.1, N 2.7, S 12.0. Ϫ M.p. 180 °C
(dec.). Ϫ 1H NMR ([D6]acetone): δ ϭ 1.2 (t, 6 H, PPhMe2), 1.4
(m, 6 H, C5H10N), 3.7 (m, 4 H, C5H10N), 7.4 (m, 3 H, PPhMe2),
7.6 (m, 2 H, PPh2Me). Ϫ 19F NMR ([D6]acetone): δ ϭ 117.0 (d,
Jom ϭ 23.5 Hz, 2 Fo), Ϫ161.3 (t, Jmp ϭ 19.2 Hz, 1 Fp), Ϫ164.1 (m,
2 Fm). Ϫ 31P{1H} NMR ([D6]acetone): δ ϭ 1.8 (s).
(aP)2 ϩ bP] where P ϭ (Fo ϩ 2Fc )/3 and a and b are constants
set by the program} over the observed reflections [I Ͼ 2σ(I)]. Crys-
tallographic data (excluding structure factors) for the structures re-
ported in this paper have been deposited with the Cambridge Crys-
tallographic Data Centre as supplementary publications no.
CCDC-139088 to CCDC-139090. Copies of the data can be ob-
tained free of charge on application to The Director, CCDC, 12
Union Road, Cambridge CB2 1EZ, UK [Fax: (internat.)
ϩ44Ϫ1223/336-033, E-mail: deposit@chemcrys.cam.ac.uk].
2
2
28: Yield 74%. Ϫ C18H25F5NNiPS2 (504.2): calcd. C 42.9, H 5.0,
N 2.8, S 12.7; found C 42.7, H 4.9, N 2.7, S 12.6. Ϫ M.p. 160 °C
(dec.). Ϫ 1H NMR ([D6]acetone): δ ϭ 1.2 (m, 15 H, PEt3), 1.7 (m,
6 H, C5H10), 3.7 (m, 4 H, C5H10). Ϫ 19F NMR ([D6]acetone): δ ϭ
Ϫ116.4 (d, Jom ϭ 24.2 Hz, 2 Fo), Ϫ161.6 (t, J
ϭ 19.6 Hz, 1 Fp),
mp
Ϫ164.2 (m, 2 Fm). Ϫ 31P{1H} NMR ([D6]acetone): δ ϭ 21.3 (s).
Acknowledgments
29: Yield 75%. Ϫ C24H21F5NNiOPS2 (588.2): calcd. C 49.0, H 3.6,
N 2.4, S 10.9; found C 48.9, H 3.7, N 2.3, S 10.7. Ϫ M.p. 147 °C
(dec.). Ϫ H NMR ([D6]acetone): δ ϭ 1.6 (m, 3 H, PPh2Me), 3.7
´
The support of this work by the Direccion General de Ensen
˜anza
´
´
Superior e Investigacion Cientıfica (project PB97Ϫ1036), Spain, is
gratefully acknowledged. J.L.S. thanks CAJAMURCIA, Spain, for
a grant.
1
(m, 8 H, C4H8O), 7.4 (m, 6 H, PPh2Me), 7.6 (m, 4 H, PPh2Me).
Ϫ
19F NMR ([D6]acetone): δ ϭ Ϫ116.9 (d, Jom ϭ 23.5 Hz, 2 Fo),
Ϫ161.4 (t, Jmp ϭ 19.8 Hz, 1 Fp), Ϫ164.1 (m, 2 Fm). Ϫ 31P{1H}
NMR ([D6]acetone): δ ϭ 15.3 (s).
[1]
P. J. Blower, J. R. Dilworth, Coord. Chem. Rev. 1987, 76,
121Ϫ185.
[2]
R. J. Angelici, Acc. Chem. Rev. 1988, 21, 387Ϫ394.
T. Yamamoto, K. Hataya, K. Osakada, Inorg. Chem. 1993,
30: Yield 79%. Ϫ C19H19F5NNiOPS2 (526.16): calcd. C 43.4, H
3.6, N 2.7, S 12.2; found C 43.3, H 3.5, N 2.6, S 12.3. Ϫ M.p. 142
[3]
32, 2360Ϫ2365.
1
[4]
°C (dec.). Ϫ H NMR ([D6]acetone): δ ϭ 1.4 (m, 6 H, PPhMe2),
P. P. Power, S. C. Shoner, Angew. Chem. Int. Ed. Eng. 1991,
3.7 (m, 8 H, C4H8O), 7.4 (m, 3 H, PPhMe2), 7.6 (m, 2 H, PPh2Me).
30, 330Ϫ332.
[5]
19F NMR ([D6]acetone): δ ϭ Ϫ117.3 (d, Jom ϭ 23.8 Hz, 2 Fo),
R. Cammack, in The Bioinorganic Chemistry of Nickel (Ed.: J.
R. Lancaster), VCH, New York, 1989, ch. 8.
A. D. Watson, Ch. P. Rao, J. R. Dorfman, R. H. Holm, Inorg.
Ϫ
Ϫ160.9 (t, Jmp ϭ 19.5 Hz, 1 Fp), Ϫ163.9 (m, 2 Fm). Ϫ 31P{1H}
NMR ([D6]acetone): δ ϭ 1.8 (s).
[6]
Chem. 1985, 24, 2820Ϫ2826.
[7]
W. Tremel, M. Kriege, B. Krebs, G. Henkel, Inorg. Chem. 1988,
31: Yield 74%. Ϫ C17H23F5NNiOPS2 (506.2): calcd. C 40.3, H 4.6,
N 2.8, S 12.7; found C 40.5, H 4.4, N 2.9, S 12.7. Ϫ M.p. 128 °C
27, 3886Ϫ3895.
[8]
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