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INTRODUCTION
Inorganic Chemistry
Article
II12
1a
Ni1N1
Ni1N2
Ni1S1
N2Ni1N1
N1Ni1S1
N2Ni1S1
1.9288(18)
1.8658(19)
2.1728(7)
96.37(7)
110.39(6)
153.08(6)
1.921(2) [1.921(2)]
1.866(2) [1.876(2)]
2.1506(8) [2.1512(8)]
96.06(10) [96.24(9)]
115.87(7) [116.09(7)]
148.03(7) [147.65(7)]
Inorganic Chemistry
Article
Inorganic Chemistry
Article
Ni1N1
Ni1N2
Ni1S1
K1S1
K1S1
K1O1
N1Ni1N2
N1Ni1S1
N2Ni1S1
1.9156(15)
1.9109(16)
2.1986(6)
3.0683(7) [3.1023(7)]b
3.0684(7) [3.1023(7)]b
2.613(2)
97.47(6)
129.56(5)
132.85(8)
1.9048(9)
1.9243(9)
2.2471(3)
3.3428(4)
3.1676(4)
2.7696(9)
98.04(4)
144.49(3)
117.24(3)
Inorganic Chemistry
Article
CONCLUSION
Inspired by the 3-fold S-ligated nickel centers found in
metalloenzymes such as the CODH or ACS, the introduction
of thiolates into the coordination spheres of [LtBuNi]+ moieties
was investigated. Complex [LtBuNi(SEt)] (1) could be accessed
displaying a three-coordinate Ni center with a T-shaped
environment. In an attempt to approach the electronic situation
provided by a cysteinate ligand more closely aminoethanethiolate was employed as a ligand, too, which led to a nickel(II)
complex with a distorted square planar ligand coordination
geometry composed of a chelating NH2(CH2)2S unit and
a diketiminate ligand in an unusual 2C,N coordination mode.
The thiolate compounds did not exhibit a pronounced reactivity
toward CO even though [LtBuNi(CO)] was found in traces.
Reduction of 1 and its benzenethiolate analogue by KC8 led to
rare examples of structurally characterized nickel(I) thiolate
complexes, which may serve as models for intermediates in the
catalytic cycle of the ACS.
EXPERIMENTAL SECTION
Inorganic Chemistry
Article
spectrometry (ESI-MS) (250 V, pos): m/z = 636.3879 ([LtBuNi(aet)+H]+, calcd: 636.3861), 658.3695 ([LtBuNi(aet)+Na]+, calcd:
658.3681); IR (KBr): = 3312 (m), 3265 (w), 3249 (w), 3056 (m),
3050 (m), 2962 (vs), 2928 (s), 2903 (s), 2868 (s), 2835 (m), 1612 (s),
1603 (s), 1586 (s), 1512 (w), 1477 (s), 1461 (s), 1441 (m), 1429 (m),
1408 (s), 1396 (s), 1383 (m), 1364 (m), 1324 (s), 1252 (m), 1214 (m),
1189 (m), 1178 (m), 1160 (w), 1122 (m), 1091 (m), 1080 (m), 1061
(s), 1039 (m), 1028 (m), 999 (s), 960 (m), 936 (m), 889 (w), 877 (m),
865 (w), 850 (m), 820 (w), 800 (s), 770 (s), 760 (s), 689 (w) cm1;
elemental analysis (%) calcd for C37H59N3NiS (636.64 g mol1):
C 69.80, H 9.34, N 6.60; found: C 69.48, H 9.41, N 6.10.
Synthesis of (KOEt2)(K)[LtBuNi(SEt)]2 (3). A dark blue hexane
solution of [LtBuNi(SEt)] (1) (100 mg, 0.16 mmol) was treated with
KC8 (23 mg, 0.17 mmol, 1.1 equiv) and stirred for 12 h. All volatiles of
the resulting red suspension were removed in vacuum. The residue was
extracted with diethyl ether (10 mL). Removal of the solvent yielded 3
as a red solid, which was dried in vacuum (73 mg, 0.05 mmol, 65%).
1
H NMR (C6D6, 300.1 MHz): = 3.5 (br), 1.1 (br) ppm; eff
(solution, C6D6, 300.1 MHz) = 2.90 B; eff (solid, r.t.) = 3.08 B, UV
vis (Et2O): max ( in mM1 cm1) = 285 (sh, 26), 315 (33), 387 (11),
450 (sh, 6), 550 (sh, 2), 700 (1) nm; IR (KBr): = 3052 (m), 3011 (m),
2958 (vs), 2905 (s), 2868 (s), 1904 (w), 1849 (w), 1618 (w), 1581 (w),
1532 (m), 1503 (s), 1463 (m), 1444 (m), 1425 (s), 1404 (vs), 1365 (s),
1324 (s), 1253 (m), 1219 (m), 1195 (m), 1184 (m), 1155 (m), 1096
(m), 1057 (w), 1040 (w), 1028 (m), 964 (w), 935 (m), 889 (m),
878 (m), 843 (w), 803 (m), 776 (m), 757 (m), 707 (w), 680 (w), 648
(w) cm1; elemental analysis (%) calcd for C78H126K2N4Ni2OS2
(1395.57 g mol1): C 67.13, H 9.10, N 4.01; found: C 66.92, H 9.00,
N 4.09.
Synthesis of (KOEt2)2[LtBuNiSPh]2 (4). A dark green hexane
solution of [LtBuNi(SPh)] (II) (100 mg, 0.15 mmol) was treated with
KC8 (22 mg, 0.16 mmol, 1.1 equiv) and stirred for 12 h. The suspension was ltered, and the solvent was evaporated under vacuum.
Crystallization from diethyl ether at 30 C yielded red crystals of 4,
which were dried in vacuum (68 mg, 0.04 mmol, 58%). 1H NMR (C6D6,
300.1 MHz): = 3.6 (br), 0.9 (br) ppm; eff (solution, C6D6, 300.1
MHz, 21 C) = 2.79 B; UVvis (Et2O): max ( in mM1 cm1) = 290
(sh, 33), 315 (41), 390 (sh, 10), 421 (sh, 9), 535 (sh, 2), 780 (1) nm; IR
(KBr): = 3052 (w), 2958 (vs), 2927 (s), 2905 (s), 2868 (m), 1620 (w),
1575 (m), 1532 (m), 1502 (m), 1460 (m), 1444 (m), 1424 (m), 1402
(vs), 1365 (s), 1323 (s), 1253 (w), 1219 (m), 1195 (w), 1184 (w), 1155
(m), 1096 (m), 1080 (m), 1024 (m), 935 (m), 889 (w), 803 (m), 777
(m), 758 (m), 740 (m), 697 (m) cm1; elemental analysis (%) calcd
for C90H136K2N4Ni2O2S2 (1565.78 g mol1): C 69.04, H 8.75, N 3.58;
found: C 69.31, H 8.84, N 3.99.
Reaction of (KOEt2)(K)[LtBuNi(SEt)]2 (3) with CO. At r.t., an
orange-red hexane suspension of (KOEt2)(K)[LtBuNi(SEt)]2 (3)
(27 mg, 19 mol) was treated with excess CO and stirred for 15 min.
The precipitation of a white solid was observed. Filtration of the
suspension* and removal of all volatile materials aorded a red-brown
solid of [LtBuNi(CO)] (10 mg, 17 mol, 44%) as revealed by a 1H NMR
spectrum of a benzene-d6 solution featuring two broad signals, which
are characteristic for the nickel(I) carbonyl compound. 1H NMR
(300.1 MHz, C6D6): = 3.4 (br), 2.9 (br) ppm; IR (KBr): = 2009
(s, CO) cm1. *1H NMR spectroscopy of a DMSO-d6 solution of the
remaining cruddy white residue proved the formation of KSEt. 1H NMR
(300.1 MHz, DMSO-d6): = 2.21 (q, 3JHH = 7.3 Hz, 2H, KSCH2CH3),
1.04 (t, 3JHH = 7.3 Hz, 3H, KSCH2CH3) ppm.
Reaction of (KOEt2)2[LtBuNi(SPh)]2 (4) with CO. At r.t., an
orange-red hexane solution of (KOEt2)2[LtBuNi(SPh)]2 (4) (39 mg,
25 mol) was treated with excess CO and stirred for 10 min. The
precipitation of a white solid was observed. All volatiles of the resulting
red-brown suspension were removed in vacuum. The residue was
extracted with hexane. Filtration* and removal of the solvent aorded a
red-brown solid of [LtBuNi(CO)] (14 mg, 24 mol, 48%) as revealed by a
1
H NMR spectrum of a benzene-d6 solution featuring two broad signals,
which are characteristic for the nickel(I) carbonyl compound. 1H NMR
(300.1 MHz, C6D6): = 3.4 (br), 2.9 (br) ppm; IR (KBr): = 2011
(s, CO) cm1. *1H NMR spectroscopy of a DMSO-d6 solution of
the remaining cruddy white residue proved the formation of KSPh.
F
Inorganic Chemistry
Article
Table 3. X-ray Structure Parameters for the Nickel(II) and Nickel(I) Thiolate Complexes Discussed in This Work
formula
fw
cryst syst
space group
a /
b /
c /
/deg
/deg
/deg
V /3
Z
calc density/g cm3
/mm1
F(000)
/deg
reections collected/unique
nal R indices [I > 2(I)]
R indices (all data)
GOF
C37H58N2NiS
621.62
triclinic
P1
9.6736(3)
9.7346(3)
41.7577(11)
95.973(2)
90.744(2)
113.835(2)
3570.81(18)
4
1.156
0.628
1352
2.3026.60
45 193/14 924 [Rint = 0.0931]
R1 = 0.0436, wR2 = 0.0908
R1 = 0.0773, wR2 = 0.0963
0.847
C37H59N3NiS
636.64
monoclinic
Pc
10.4799(4)
14.9728(5)
11.5528(4)
90
107.423(3)
90
1729.62(11)
2
1.222
0.650
692
3.2927.90
19 613/7951 [Rint = 0.0363]
R1 = 0.0252, wR2 = 0.0507
R1 = 0.0294, wR2 = 0.0515
1.020
C78H126K2N4Ni2OS2
1395.57
orthorhombic
Pbcn
26.4765(15)
17.9487(10)
16.7544(9)
90
90
90
7962.0(8)
4
1.164
2.329
3024
2.9766.73
58 562/7010 [Rint = 0.0508]
R1 = 0.0355, wR2 = 0.0837
R1 = 0.0542, wR2 = 0.0925
1.010
C90H136K2N4Ni2O2S2
1565.77
monoclinic
P21/n
12.7088(4)
18.3156(6)
19.4283(6)
90
102.5970(10)
90
4413.5(2)
2
1.178
0.615
1692
2.4228.34
152 169/10 977 [Rint = 0.0631]
R1 = 0.0326, wR2 = 0.1158
R1 = 0.0377, wR2 = 0.1229
1.035
H NMR (300.1 MHz, DMSO-d6): = 6.98 (d, 3JHH = 6.9 Hz, 2H,
Ar-oH), 6.63 (t, 3JHH = 7.3 Hz, 2H, Ar-mH), 6.39 (t, 3JHH = 7.6 Hz, 1H,
Ar-pH) ppm.
Crystal Structure Determinations. The data collections (see
Table 3) were performed with a STOE IPDS 2T (1 and 2) or with a
BRUKER D8 Venture (3 and 4) diractometer at 100 K by using Mo K
(1, 2, 4, = 0.710 73 ) and Cu K (3, = 1.541 78 ) radiation. The
structures were solved by direct methods (SHELXS-97)33 and rened
by full-matrix least-squares procedures based on F2 with all measured
reections (SHELXL-97,34 SHELXL-201335). All non-hydrogen atoms
were rened anisotropically. All hydrogen atoms were added geometrically and rened by using a riding model. Additional crystallographic
data, including CIF les, can be found in the Supporting Information.
1
ASSOCIATED CONTENT
S Supporting Information
*
Additional spectroscopic data, ESI mass spectra, DFT calculations, and X-ray crystallographic data in cif format. This
material is available free of charge via the Internet at http://pubs.
acs.org. CCDC 984793 (1), CCDC 984794 (2), CCDC 984795
(3), and CCDC 984796 (4) contain the supplementary
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.
REFERENCES
AUTHOR INFORMATION
Corresponding Author
*E-mail: Christian.limberg@chemie.hu-berlin.de.
Notes
ACKNOWLEDGMENTS
We are grateful to the Cluster of Excellence Unifying Concepts
in Catalysis funded by the Deutsche Forschungsgemeinschaft
(DFG) as well as the Humboldt-Universitat zu Berlin for
nancial support. Dr. S. Mebs is thanked for the X-ray analysis
of 1. We also thank C. Matlachowski and S. T. Li for EPR
measurements.
G
Inorganic Chemistry
Article