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(
1
ESI): calcd. for
596.4670. μeff (CDCl ) = 3.03 μ .
C
92
H
80CrN12
O
6
Ti
2
1596.4682 [M]+; found
Hashimoto, J. Am. Chem. Soc. 2007, 129, 9596–9597; h) H.
Irie, S. Miura, R. Nakamura, K. Hashimoto, Chem. Lett. 2008,
3 B
3
7, 252–253; i) T. Takashima, A. Yamaguchi, K. Hashimoto,
[
(tmtaa)Ti=OǞCr(tfp)ǟO=Ti(tmtaa)]SbF
was synthesized and purified by following a procedure similar to
that described above for by using [Cr(tfp)Cl] (47.5 mg,
.062 mmol), [(tmtaa)Ti=O] (50.0 mg, 0.12 mmol), NaSbF
6 :
(10) Compound 10
R. Nakamura, Chem. Commun. 2012, 48, 2964–2966; j) A. Ok-
amoto, R. Nakamura, H. Osawa, K. Hashimoto, J. Phys.
Chem. C 2008, 112, 19777–19783.
4
0
6
[3] a) T. Cuk, W. W. Weare, H. Frei, J. Phys. Chem. C 2010, 114,
9167–9172; b) N. Sivasankar, W. W. Weare, H. Frei, J. Am.
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naughtan, W. W. Weare, J. Yano, H. Frei, J. Phys. Chem. C
(
(
17.5 mg, 0.068 mmol), and a 1:1 acetonitrile/toluene mixture
8 mL). X-ray-quality crystals were prepared similarly to 2, yield
after recrystallization: 42.9 mg, 40%. UV/Vis (CH
3
2 2
Cl ): λmax (ε) =
2
011, 115, 24893–24905; d) B. A. McClure, H. Frei, J. Phys.
47 (54181), 391 (58700), 424 (32000), 454 (62400), 526 (5400), 577
Chem. C 2014, 118, 11601–11611.
7000), 613 (8400), 635 nm (6300 m–1 cm ). C88
CH Cl : C 52.01, H 3.61, N 8.94; found C 52.04, H 3.54, N 8.77.
FTIR (ATR): ν˜ = 894 (s, Ti=O), 654 (Sb–F) cm . HRMS (ESI):
–1
(
4
12 2 2
H68CrF10N O SbTi ·
[
4] P. W. Wanandi, W. M. Davis, C. C. Cummins, M. A. Russell,
D. E. Wilcox, J. Am. Chem. Soc. 1995, 117, 2110–2111.
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2
2
–1
[
+
calcd. for C88
μ
H
68CrF
4
N
12
O
2
Ti
2
1548.3883 [M] ; found 1548.3857.
19, 235–251.
eff (CD Cl ) = 3.37 μ
2
2
B
.
[6]
K. Bhattacharya, M. Maity, D. Mondal, A. Endo, M. Chaud-
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[
(tmtaa)Ti=OǞCr(tfmp)ǟO=Ti(tmtaa)]SbF (11): Compound 11
6
[
[
[
[
was synthesized and purified by following a procedure similar to
that described above for 4 by using [Cr(tfmp)Cl] (60.3 mg,
0
.062 mmol), [(tmtaa)Ti=O] (50.0 mg, 0.12 mmol), NaSbF
6
17.5 mg, 0.068 mmol), and a 1:1 acetonitrile/toluene mixture
3 mL), yield after recrystallization: 43.5 mg, 37%. UV/Vis
(
(
(
(
(
CH
2 2
Cl ): λmax (ε) = 347 (60700), 391 (60000), 424 (33000), 454
–1
–1
66000), 527 (3700), 578 (5800), 612 nm (6100 m cm ). FTIR
–1
ATR): ν˜ = 906 (s, Ti=O), 657 (Sb–F) cm . C92
CH Cl
HRMS (ESI): calcd. for C92
H
12 2 2
68CrF18N O Ti ·
4
2
2
: C 49.60, H 3.30, N 7.23; found C 49.13, H 3.63, N 6.53.
+
H
68CrF12
N
12
O
2
Ti
2
1748.3755[M] ;
–
found 1748.3729. HRMS (ESI): calcd. for SbF
found 234.8938. μeff (CD Cl ) = 3.11 μ
6
234.8948 [M] ;
2
2
B
.
[
12] A. J. Falzone, J. Nguyen, W. W. Weare, R. D. Sommer, P. D.
[
(tmtaa)Ti=OǞCr(tfmp)ǟO=Ti(tmtaa)][ClH
pound 12 was synthesized by following a procedure similar to that
described above for 4 by using 7 (25 mg, 0.014 mmol), H tfmp
18.7 mg, 0.021 mmol), [(tmtaa)Ti=O] (5.7 mg, 0.014 mmol), and a
4
tfmp] (12): Com-
Boyle, Chem. Commun. 2014, 50, 2139–2141.
[
[
13] I. Vernik, D. V. Stynes, Inorg. Chem. 1998, 37, 10–17.
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4
(
1
:1 acetonitrile/toluene mixture (8 mL). Pure 12 was obtained as
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orange plates after slow cooling of the mixture. Crude yield:
9
5
.1 mg, 25%. UV/Vis (CH
77, 611 nm. FTIR (ATR): ν˜ = 906 (s, Ti=O) cm . HRMS (ESI):
Ti 1748.3755; found 1748.3762.
2 2
Cl ): λmax = 343, 392, 425, 455, 529,
–1
calcd. for C92
HRMS (ESI): calcd. for C48
27.2141.
H
68CrF12
N
12
O
2
2
–
H
4
32ClF12N 927.2129 [M] ; found
9
[
16] a) C. E. Housmekerides, R. S. Pilato, G. L. Geoffroy, A. L.
Supporting Information (see footnote on the first page of this arti-
cle): Details of synthesis of the anion trap (H tfmp), titration ex-
periments and use of the Hills equation, electrochemistry experi-
ments, X-ray crystallographic data, SQUID experiments, solid-state
ATR-FTIR spectrum, and molar extinction coefficients of 1–12.
Rheingold, J. Chem. Soc., Chem. Commun. 1991, 563; b) C. E.
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4
[
[
[
[
[
[
[
17] R. E. Haddad, S. Gazeau, J. Pecaut, J. C. Marchon, C. J. Med-
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Acknowledgments
This work was supported by start-up funding from North Carolina
State University. The authors acknowledge Xiao Song and Prof.
Tatyana Smirnova for assistance in collecting EPR spectra. We
acknowledge Daniel Stasiw and Prof. David Shultz for assistance in
collecting SQUID data. Mass spectra were obtained at the NCSU
Department of Chemistry Mass Spectrometry Facility.
20] C. L. Hill, F. J. Hollander, J. Am. Chem. Soc. 1982, 104, 7318–
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V. M. Lynch, P. A. Gale, J. L. Sessler, J. Am. Chem. Soc. 1999,
121, 11020–11021; c) K. Liu, J. Xu, Y. Sun, Y. Guo, S. Jiang,
S. Shao, Spectrochim. Acta Part A 2008, 69, 1201–1206; d)
N. G. Giri, S. M. Chauhan, Spectrochim. Acta Part A 2009, 74,
297–304; e) S. Fukuzumi, K. Ohkubo, F. D’Souza, J. L. Sessler,
Chem. Commun. 2012, 48, 9801–9815.
[
[
1] B. O. West, Polyhedron 1989, 8, 219–247.
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H. Frei, Microporous Mesoporous Mater. 2007, 103, 265–272;
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Eur. J. Inorg. Chem. 2014, 5662–5674
5673
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