Inorganic Chemistry
Article
of acetone followed by a slurry of Fe(pdt)(CO)2(dppbz) (0.066 g, 0.1
mmol) also in 10 mL of acetone. The mixture immediately became
dark brown. After stirring the mixture for 2 h at 0 °C, solvent was
removed under a vacuum. The solid residue was extracted into
CH2Cl2, and this extract was filtered through glass wool. The filtrate
was evaporated to give a brown-colored solid. Crystals were obtained
from vapor diffusion of pentane into a CH2Cl2 solution of the salt at
−30 °C. Yield: 115 mg (95%). IR (CH2Cl2): νCO = 1946 cm−1. ESI-
MS (positive, CH2Cl2): 1124.1044 [M]+, 1096.1278 [M-CO]+. 31P
NMR (202 MHz, CH2Cl2): δ72.66 (dd, 1P, Fe−P), 67.80 (dd, 1P,
Fe−P), 19.43 (dd, 1P, Ni−P). 1H NMR (500 MHz, CD2Cl2): δ7.76−
6.54 (overlapping signals, 43H), 3.80 (s, 3H), 3.62 (dt, J = 13.73, 4.58
Hz, 1 H), 2.89 (d, J = 13.73 Hz, 1 H), 2.27 (d, J = 13.73 Hz, 1 H),
2.01−2.10 (m, 1 H), 1.92−2.01 (m, 1 H), 1.86 (d, J = 7.63 Hz, 1 H).
Anal. Calcd for C62.5H57BCl6F4FeNNiO2P3S2 [[(PCHNAn)Ni(μ-
pdt)ClFe(dppbz)(CO)]BF4·2.5CH2Cl2] (found): C, 52.67 (52.39);
H, 4.03 (4.2); N, 0.98 (1.0).
additional CH2Cl2 as an eluent. The brown-colored band was
collected and reduced in volume. Addition of 60 mL of pentane to the
concentrated CH2Cl2 solution precipitated [(dppv)(CO)Fe(μ-
pdt)]2Ni as a brown solid. Yield: 0.362 g (35%). Vapor diffusion of
pentane into a concentrated solution of [(dppv)(CO)Fe(μ-pdt)]2Ni
in CH2Cl2 gave red-orange prisms suitable for X-ray crystallography.
1H NMR (500 MHz, C6D6): δ 8.34 (br s, 8H), 7.74−7.55 (m, 12H),
7.32 (br s, 8H), 7.11 (m, 4H), 7.03 (m, 8H), 6.97 (m, 4H), 2.16−
1.77 (m, 8H), 1.32−1.07 (m, 4H). 31P{1H} NMR (202 MHz, C6D6):
δ100.19 (br s, 2P), 81.51 (br s, 2P). IR (THF): νCO = 1914 (s) cm−1.
Anal. Calcd for C60H58Fe2NiO2P4S4: C, 58.42; H, 4.74. Found: C,
57.65; H, 4.44.
{H[(dppv)(CO)Fe(μ-pdt)]2Ni]}BF4. A solution of [(dppv)(CO)-
Fe(μ-pdt)]2Ni (200 mg, 1.62 × 10−4 mmol, 1 equiv) in 4 mL of
CH2Cl2 was treated with HBF4•Et2O (22 μL, 26 mg, 1.62 × 10−4
mol, 1 equiv). The mixture was stirred at room temperature for 30
min. A dark red solution developed. The solvent was removed under a
vacuum. The solid residue was washed with dry Et2O (3 × 5 mL) and
dried under a vacuum. Crystals of this were grown by vapor diffusion
of pentane into CH2Cl2 solutions of the salt at room temperature.
Yield: 152 mg (71%). 1H NMR (500 MHz, CD2Cl2, basal−basal
isomer, −60 °C): δ 8.27 (ddd, J = 85, 45, 12 Hz, 4H), 7.73 (s, 4H),
7.32 (br s, 8H), 7.64−7.05 (m, 36H), 2.52−1.22 (overlapping signals,
6H), 1.10 (s, 2H), 0.31 (br s, 1H), 0.25 (br s, 2H), −0.28 (br s, 1H),
[(PCHNAn)Ni(μ-pdt)(H)Fe(dppbz)(CO)]BF4. A solution of
Cp*2Co (0.066 g, 0.2 mmol) in 5 mL of THF was added into a
slurry of [(PCHNAn)Ni(μ-pdt)ClFe(dppbz)(CO)]BF4 (0.121 g,
0.1 mmol) in 5 mL of THF. The resulting mixture was stirred for 2 h
at room temperature. The yellow solid precipitate ([Cp*2Co]Cl/
[Cp*2Co]BF4) was filtered off. The filtrate was evaporated to dryness
to obtain the (PCHNAn)Ni(μ-pdt)Fe(dppbz)(CO) as a brown
solid. This compound is soluble in THF, toluene, and CH2Cl2. IR
(CH2Cl2): νCO = 1919 cm−1. 31P NMR (202 MHz, THF): δ88.35
1
−5.10 (br s, 1H). H NMR (500 MHz, CD2Cl2, mixture of isomers,
20 °C): δ 8.56−7.05 (overlapping signals, 40H), 2.48 (m, 0.74 H),
2.04 (t, J = 13 Hz, 0.91H). 1.97 (m, 0.44H), 1.75 (m, 2.75H), 1.59
(m, 1.31H), 1.27 (m, 0.8H), 1.15 (m, 0.75H), 1.08 (m, 1.36H), 0.82
(m, 1.63H), 0.51 (m, 0.49H), 0.27 (m, 0.77H), −0.15 (q, J = 13 Hz),
−4.87 (t, J = 38 Hz, 0.15H), −6.67 (br s, 0.23H), −15.50 (s, 0.36H).
31P{1H} NMR (202 MHz, CD2Cl2, 20 °C): δ95.23 (br s, 2P, apical-
basal isomer), 91.49 (br s, 2P, apical-basal isomer), 87.43 (s, 4P, Ni−
H), 86.72 (s, 2P, basal−basal isomer), 71.70 (s, 2P, basal−basal
isomer). IR (THF): νCO = 1965, 1943 cm−1. Anal. Calcd for C61H59B
Cl2F4Fe2NiO2P4S4: C, 52.17; H, 4.23. Found: C 52.09; H. 4.35
1
(dd, 1P, Fe−P), 80.74 (dd, 1P, Fe−P), 36.13 (q, 1P, Ni−P). H
NMR (500 MHz, THF-d8): δ8.22−6.16 (overlapping signals, 43H),
3.49 (s, 3H), 2.17 (m, 1H), 1.92 (m, 1H), 1.84 (m, 1H), 1.66 (m,
1H), 1.13 (m, 1H), 1.04 (m, 1H). Crude (PCHNAn)Ni(μ-
pdt)Fe(dppbz)(CO) (0.087 g, 0.08 mmol) was dissolved in 10 mL of
THF, and HBF4·Et2O (11 μL, 0.08 mmol) was added dropwise to this
solution. The resulting dark brown mixture was stirred for 2 h. The
solvent was evaporated to dryness to obtain [(PCHNAn)Ni(μ-
pdt)(H)Fe(dppbz)(CO)]BF4. Crystals were obtained upon vapor
diffusion of pentane into CH2Cl2 solution of the salt. Yield: 85 mg
(90%). IR (CH2Cl2): νCO = 1945 cm−1. ESI-MS (positive, CH2Cl2):
1090.1417 [M]+, 1062.1503 [M-CO]+. 31P NMR (202 MHz, THF):
δ94.47 (1P, Fe−P), 91.58 (1P, Fe−P), 76.78−77.30 (2P, Fe−P),
28.01 (d, 1P, Ni−P), 21.50 (t, 1P, Ni−P). 31P NMR (202 MHz,
CD2Cl2): δ 94.55 (1P, Fe−P), 91.01 (1P, Fe−P), 75.83 (0.5P, Fe−P),
72.92 (0.5P, Fe−P), 26.75 (1P, Ni−P), 19.83 (0.5P,Ni−P). 1H NMR
(CD2Cl2): −0.66 (t, hydride, 1H). Anal. Calcd for C61H55BCl2F4-
FeNNiO2P3S2 [[(PCHNAn)Ni(μ-pdt)(H)Fe(dppbz)(CO)]BF4·
CH2Cl2] (found): C, 57.99 (58.13); H, 4.39 (5.05); N, 1.11 (1.12).
[(PCH2NHAn)Ni(μ-pdt)ClFe(dppbz)(CO)]BF4. A slurry of Fe-
(pdt)(CO)2(dppbz) (0.066 g, 0.1 mmol) in 10 mL of acetone was
treated with a slurry of [NiCl2(PCH2NHAn)]2 (0.050 g, 0.05 mmol)
in 10 mL of acetone and a solution of NaBF4 (0.017 g, 0.15 mmol)
also in 10 mL of acetone. The solution immediately turned dark
brown. The resulting mixture was stirred for 2 h at 0 °C. Solvent was
removed, and the solid residue was extracted with CH2Cl2. After
filtering through glass wool, this extract was evaporated, leaving
{H[(dppv)(CO)Fe(μ-pdt)]2Ni]}BArF was prepared similarly. 1H
4
NMR (500 MHz, CD2Cl2, mixture of isomers, 20 °C): δ 8.56−7.05
(overlapping signals, 48H), 2.48 (m, 0.74 H), 2.04 (t, J = 13 Hz,
0.91H). 1.97 (m, 0.44H), 1.75 (m, 2.75H), 1.59 (m, 1.31H), 1.27 (m,
0.8H), 1.15 (m, 0.75H), 1.08 (m, 1.36H), 0.82 (m, 1.63H), 0.51 (m,
0.49H), 0.27 (m, 0.77H), −0.15 (q, J = 13 Hz), −4.87 (t, J = 38 Hz,
0.15H), −6.67 (br s, 0.23H), −15.50 (s, 0.36H). 31P{1H} NMR (202
MHz, CD2Cl2, 20 °C): 95.23 (br s, 2P, apical-basal isomer), 91.49 (br
s, 2P, apical-basal isomer), 87.43 (s, 4P, Ni−H), 86.72 (s, 2P, basal−
basal isomer), 71.70 (s, 2P, basal−basal isomer). IR (THF): νCO
=
1965, 1943 cm−1.
(C6F5)2Ni(μ-pdt)Fe(CO)2(dppv). In the glovebox a solution of
Fe(pdt)(CO)2(dppv) (370.0 mg, 0.602 mmol) in 30 mL of THF was
added dropwise to a stirred solution of Ni(C6F5)2(dioxane)2 (342.5
mg, 0.602 mmol) in 10 mL of THF over 20 min at room temperature.
The solution quickly changed from orange to a very dark red. The
reaction was judged complete based on 31P NMR measurements. The
volume of the reaction mixture was reduced to ∼10 mL under
vacuum. Addition of 20 mL of pentane to this filtrate produced a
bright red powder. Slow diffusion of pentane into a THF solution of
the complex resulted in long ruby-red needles. Yield: 480 mg (79%).
1H NMR (500 MHz, THF-d8, 20 °C): δ8.56−7.05 (overlapping
signals, 48H), 2.48 (m, 0.74 H), 2.04 (t, J = 13 Hz, 0.91H). 1.97 (m,
0.44H), 1.75 (m, 2.75H), 1.59 (m, 1.31H), 1.27 (m, 0.8H), 1.15 (m,
0.75H), 1.08 (m, 1.36H), 0.82 (m, 1.63H), 0.51 (m, 0.49H), 0.27 (m,
0.77H), −0.15 (q, J = 13 Hz), −4.87 (t, J = 38 Hz, 0.15H), −6.67 (br
s, 0.23H), −15.50 (s, 0.36H). 19F{1H} NMR (470.4 MHz, THF-d8,
20 °C): δ119.2 (d, J = 30.8 Hz, 2F), 120.8 (d, J = 30.8 Hz, 2F),
169.75 (t, J = 20.2 Hz, 2F), 171.0 (br, 2F), 171.2 (br, 2F). 31P{1H}
brown-black solid product. Yield: 110 mg (91%). IR (CH2Cl2): νCO
=
1949 cm−1. ESI-MS (positive, CH2Cl2): 1126.1201 [M]+, 1098.1071
[M-CO]+. 31P NMR (202 MHz, CH2Cl2): δ74.07 (dd, 1P, Fe−P),
1
71.43 (dd, 1P, Fe−P), −3.25 (dd, 1P, Ni−P). H NMR (500 MHz,
CD2Cl2): δ7.82−6.50 (overlapping signals, 42H), 3.89−4.05 (m, 2
H), 3.78 (s, 3H), 3.50 (m, 1 H), 3.04 (m, 1 H), 2.49 (d, J = 9.16 Hz,
1 H), 2.04 (m, 1 H), 1.90 (m, 1 H), 1.44 (m, 1 H), 0.62 (d, J = 7.63
Hz, 1 H). Anal. Calcd for C61H56BCl3F4FeNNiO2P3S2
[[(PCH2NHAn)Ni(μ-pdt)ClFe(dppbz)(CO)]BF4·CH2Cl2] (found):
C, 56.37 (56.32); H, 4.34 (4.56); N, 1.08 (1.18).
[(dppv)(CO)Fe(μ-pdt)]2Ni. To a solution of Fe(pdt)-
(CO)2(dppv) (1.02 g, 1.66 mmol, 1 equiv) in 10 mL of THF was
added a solution of Ni(o-tol)Cl(tmeda) (0.50 g, 1.66 mmol, 1 equiv)
in 5 mL of THF. The reaction was stirred at room temperature for 8
h. A dark brown solution developed. The solvent was removed under
a vacuum. The solid residue was extracted into 3 mL of CH2Cl2, and
this extract was filtered through a 5 × 15 cm column of silica gel using
NMR (202 MHz, d8-THF, 20 °C): δ70.5 (s, 2P). IR (THF): νCO
=
2059, 1990 cm−1. Anal. Calcd for C43H28F10FeNiO2P2S2: C, 51.27; H,
2.80. Found: C 50.95; H. 3.00.
X-ray Crystallographic Determinations. Crystallographic Data
for Ph4P[Ni(NS3)], [Cp(CO)Fe(μ-pdt)Ni(dppbz)]BF4, [(R,R-
DIPAMP)Ni(μ-pdt)(H)Fe(CO)3]BArF , [NiCl2(PCHNAn)]2,
4
K
Inorg. Chem. XXXX, XXX, XXX−XXX