Article
(Bu4N)[Ni(pdtc)I]. Compound 5 (150 mg, 0.293 mmol) and
Inorganic Chemistry, Vol. 48, No. 13, 2009 6161
in acetonitrile (5 mL). The solution was diffused with ether to
deposit dark red block-like crystals (33 mg, 21%). Absorption
spectrum (CH2Cl2): λmax(εM) 478 (14000) nm. 1H NMR
(CD3CN): δ 7.57 (d, 6), 7.97 (t, 3). Anal. Calcd for
C37H49N5Ni3O6S7: C, 41.91; H, 4.66; N, 6.60. Found: C,
40.49; H, 4.41; N, 6.37.
Bu4NI (216 mg, 0.586 mmol) were mixed and stirred in acetone
(18 mL) for 40 min. The red solution was filtered and solvent was
removed to leave a red paste, which was dissolved in a small
amount of THF and the solution was filtered. Ether was added
to the filtrate to deposit a red oil. The oil was dissolved in
acetone (3 mL), and ether was added to make a saturated
solution, which was allowed to stand at room temperature for
30 min. The product was isolated as dark red crystals. The
filtrate was treated with ether, and the procedure repeated until
no more crystals were obtained (combined yield 220 mg, 60%).
1H NMR (CDCl3): δ 7.68 (d, 2), 7.96 (t, 1).
Method B. A solution of (Et4N)[12] (40 mg, 0.021 mmol) in
acetonitrile (20 mL) was refluxed in air for 8 h. The solution
volume was reduced to 5 mL. Diffusion of ether into this
solution caused separation of dark red block-like crystals
(26 mg, 78%) whose spectroscopic properties and cell para-
meters are identical to those of Method A.
(Bu4N)[Ni(pdtc)(OAc)]. Compound 5 (19 mg, 0.037 mmol)
and Bu4N(OAc) (22 mg, 0.074 mmol) were mixed and stirred in
acetonitrile (2 mL) for 1 h. The solution was filtered, and the
filtrate was diffused with ether to deposit the product as plate-
like orange-red crystals (22 mg, 53%). Absorption spectrum
(CH2Cl2): λmax(εM) 325 (3850), 426 (2320), 507 (710) nm. H
NMR (CDCl3): δ 2.02 (s, 3), 7.50 (d, 2), 7.82 (t, 1).
(Et4N)[Ni(pdtc)(CH2CN)]. To a solution of (Et4N)[7]
(41 mg, 0.097 mmol) in acetonitrile (2 mL) was added a solution
of NaOSiMe3 (11 mg, 0.097 mmol) in acetonitrile (1 mL). The
mixture was stirred for 2 h and filtered. Ether (18 mL) was added
to the dark red filtrate to deposit a brown precipitate, which was
dissolved in acetonitrile (2 mL) and diffused with ether to give
product as dark red crystals (26 mg, 63%). Absorption spectrum
1
1
(Et4N)[Ni(pdtc)(OSiMe3)]. To a solution of compound 7
(160 mg, 0.38 mmol) in dichloromethane was added a solution
of NaOSiMe3 (43 mg, 0.38 mmol) in dichloromethane (2 mL).
The mixture was stirred for 90 min and filtered to give a dark-red
solution. Hexane (18 mL) was added to deposit a red paste
which was taken up in dichloromethane (5 mL). The solution
was saturated with ether and stored at -30 °C overnight to
deposit red needle crystals, which were collected by decantation.
The process was repeated until no further product was obtained
(combined yield 81 mg, 45%). Absorption spectrum (CH2Cl2):
(CH2Cl2): λmax(εM) 454 (7790) nm. H NMR (CDCl3): δ 0.67
(s, 2), 7.67 (d, 2), 7.89 (t, 1). Anal. Calcd for C17H25N3NiO2S2: C,
47.90; H, 5.91; N, 9.86. Found: C, 47.32; H, 5.38; N, 9.66.
(Et4N)[Ni(pdtc)(CH2COMe)]. The previous procedure
was followed with acetone instead of acetonitrile. The reaction
mixture was stirred for 50 min. The product was isolated as a
dark red microcrystalline solid (36 mg, 84%). Absorption
spectrum (CH2Cl2): λmax(εM) 467 (8900) nm. 1H NMR (CDCl3):
δ 1.70 (s, 2), 2.11 (s, 3), 7.64 (d, 2), 7.86 (t, 1).
(Et4N)[Ni(pdtc)(CN)]. Compound 5 (100 mg, 0.20 mmol)
and Et4N(CN) (61 mg, 0.39 mmol) were mixed and stirred in
acetonitrile (3 mL) for 2 h. The red solution was filtered;
diffusion of ether into the filtrate yielded the product as red
λ
max(εM) 327 (5860), 444 (5140), 534 (2200) nm. 1H NMR
(CDCl3): δ -0.03 (s, 9), 7.43 (d, 2), 7.79 (t, 1).
(Et4N)[Ni(pdtc)(SH)]. Compound 5 (143 mg, 0.28 mmol)
and Et4N(SH) (91 mg, 0.56 mmol) were mixed and stirred in
acetonitrile (7 mL) for 1 h. The solution was filtered and diffused
with ether to deposit deep-red crystals (169 mg, 72%). Absorp-
tion spectrum (CH2Cl2): λmax(εM) 461 (9200), 548 (3940) nm. 1H
NMR (CDCl3): δ -1.99 (s, 1), 7.69 (d, 2), 7.91 (t, 1); (CD3CN):
δ -2.45 (s, 1), 7.63 (d, 2), 8.03 (t, 1). Anal. Calcd for
C15H24N2NiO2S3: C, 42.97; H, 5.77; N, 6.68; S, 22.94. Found:
C, 43.66; H, 5.54; N, 6.90; S, 22.59.
block-like crystals (121 mg, 75%). IR (KBr): vCN 2115 cm-1
.
Absorption spectrum (CH2Cl2): λmax(εM) 402 (3700), 421
1
(3600), 544 (470) nm. H NMR (CD3CN): δ 7.65 (d, 2), 8.06
(t, 1). Anal. Calcd for C16H23N3NiO2S2: C, 46.62; H, 5.62; N,
10.19. Found: C, 46.63; H, 5.38; N, 10.22. E1/21-,2- = -1.36 V
(acetonitrile).
[Ni(pdtc)(Pri2NHCMe2)] 0.25THF. Compound 5 (36 mg,
3
0.070 mmol) and Pri2NHCMe2 (25 mg, 0.140 mmol) were
23
(Et4N)[Ni(pdtc)SEt]. Compound 5 (60 mg, 0.12 mmol) and
Et4N(SEt) (45 mg, 0.23 mmol) were mixed and stirred in
acetonitrile (2 mL) for 90 min. The solution was filtered, and
the filtrate was saturated with ether. The red solution was stored
at -30 °C overnight to deposit dark red crystals. This material
was collected; ether was diffused into the filtrate to produce a
second crop of crystals (combined yield 68 mg, 65%). Absorp-
tion spectrum (CH2Cl2): λmax(εM) 315 nm (10700), 441 (8950)
mixed and stirred in THF (6 mL) for 65 h. The solution was
filtered, and the filtrate was saturated with hexane to give a red
solution with a small amount of red oil, which was removed by
filtration. The filtrate was stored at -30 °C for 3 d to deposit the
product as red crystals (18 mg, 28%). Absorption spectrum
(CH2Cl2): λmax(εM) 310 nm (3740), 404 (3550), 423 (3550), 548
1
(500) nm. H NMR (CDCl3): δ 1.65 (d, 12), 2.17 (s, 6), 6.16
(m, 2), 7.79 (d, 2), 8.00 (t, 1). E1/20,1- = -1.37 V (acetonitrile).
[Ni(pdtc)(PEt3)]. To a suspension of compound 5 (42 mg,
0.082 mmol) in dichloromethane (2 mL) was added a solution
of PEt3 (19 mg, 0.164 mmol) in dichloromethane (1 mL).
The mixture was stirred for 30 min to give a red solution. The
solution was filtered, and the filtrate was layered with hexane to
deposit red block-like crystals (44 mg, 72%). Absorption spec-
trum (CH2Cl2): λmax(εM) 398 (5100), 421 (4700), 553 (700) nm.
1
nm. H NMR (CD3CN): δ 1.44 (t, 3), 1.99 (m, 2), 7.64 (d, 2),
8.05 (t, 1).
(Et4N){[Ni(pdtc)]2SEt} CH2Cl2. (Et4N)[13] (38 mg, 0.085
3
mmol) and [Fe(Me6tren)OTf](OTf)22 (50 mg, 0.085 mmol) were
mixed and stirred in acetonitrile (3 mL) for 2.5 h. The solution
was filtered and ether (18 mL) added to deposit a red paste,
which was washed with THF (2 ꢀ 5 mL) and dissolved in
dichloromethane (6 mL) to give a red solution. Diffusion of
ether into this solution caused separation of the product as a red
crystalline solid (18 mg, 54%). Absorption spectrum (CH2Cl2):
1H NMR (CDCl3): δ 1.28 (m, 9), 1.76 (m, 6), 7.83 (d, 2),
8.04 (t, 1). 31P NMR (CDCl3): δ 26.03. E1/2
(acetonitrile).
[Ni(pdtc)CNFe(Me6tren)](OTf) CH2Cl2. To a solution
= -1.21 V
0,1-
λ
(t, 3), 2.12 (m, 2), 7.68 (d, 4), 7.94 (t, 2).
max(εM) 314 (15200), 441 (12800) nm. 1H NMR (CDCl3): δ 1.48
3
of (Et4N)[18] (40 mg, 0.097 mmol) in dichloromethane (3 mL)
was added dropwise a solution of [Fe(Me6-tren)(OTf)](OTf) (57
mg, 0.097 mmol) in dichloromethane (2 mL). The mixture was
stirred at room temperature for 3 h and filtered to give a deep-
red solution. Addition of ether (15 mL) led to a red precipitate,
which was washed with chloroform (5 mL) and dissolved in
dichloromethane (10 mL). The solution was filtered, and the
(Et4N)2{[Ni(pdtc)]3S}). Method A. To a suspension of
compound 5 (115 mg, 0.23 mmol) in acetone (25 mL) was added
dropwise a solution of 25% Et4NOH in methanol (0.40 mL, 0.58
mmol). The mixture was stirred for 2 h to give a red solution. The
solution was filtered, and the filtrate was reduced to a dark red
oil, which was washed with chloroform (3 ꢀ 5 mL) and taken up
(22) Britovsek, G. J. P.; England, J.; White, A. J. P. Inorg. Chem. 2005, 44,
8125–8134.
(23) Kuhn, N.; Kratz, T. Synthesis 1993, 561–562.