Inorganic Chemistry
Article
(overlapping, 10H total, 2H, [C3]CH2N, 4H, [C2]CH2N and 4H,
NCH2CHCHZr), 2.91 (m, 2H, [C2]CH2N), 2.77−2.63 (over-
lapping, 4H total, [C3]CH2N), 2.36 (m, 2H, [C2]CH2N), 2.17 (m, 2H,
[C3]CH2N), 1.75 (m, 2H, CH2CH2CH2), 1.52 (m, 2H,
CH2CH2CH2). 13C{1H} NMR (C6D6, 75.5 MHz, 296 K): δ (ppm)
187.2 (NCH2CHCHZr), 142.1 (NCH2CHCHZr), 66.0
(NCH2CHCHZr), 59.9 ([C2]CH2N), 56.0 ([C2]CH2N), 54.2
([C3]CH2N), 53.7 ([C3]CH2N), 26.4 (CH2CH2CH2). Anal. Calcd for
C16H28N4Zr: C, 52.27; H, 7.68; N, 15.24. Found: C, 52.13; H, 7.72; N,
15.19.
1.60 (m, 2H, CH2CH2CH2), 1.07 (m, 2H, CH2CH2CH2). 13C{1H}
NMR (C6D6, 75.5 MHz, 296 K): δ (ppm) 164.4 (i-PhOZr), 132.8 (Ph),
132.7 (i-PhCH2N), 129.7 (m-PhOZr), 128.2 (Ph), 119.9 (Ph), 118.2
(p-PhOZr), 56.6 ([C3]CH2N), 56.4 (PhCH2N), 54.5 ([C3]CH2N),
52.3 ([C2]CH2N), 48.3 ([C2]CH2N), 25.0 (CH2CH2CH2).
(Bn2Cyclam)Zr(SPh)2 (19). In a J-Young NMR tube, thiophenol (20
mg, 0.18 mmol) was added to a C6D6 solution of 16 (42 mg, 0.090
mmol). Full conversion was observed by NMR after 15 min. 1H NMR
(C6D6, 300.1 MHz, 296 K): δ (ppm) 7.74 (d, 3JH−H = 8 Hz, 4H, PhSZr),
7.19−6.95 (overlapping, 16H total, 10H, PhCH2N and 6H, PhSZr),
4.95 (d, JA‑B = 14 Hz, 2H, PhCH2N), 4.63 (d, JA‑B = 14 Hz, 2H,
PhCH2N), 4.58 (m, 2H, [C3]CH2N), 3.68 (m, 2H, [C3]CH2N), 3.61
(m, 2H, [C2]CH2N), 2.79−2.66 (overlapping, 6H total, 2H,
[C3]CH2N and 4H, 2x[C2]CH2N), 2.35−2.26 (overlapping, 4H
total, 2H, [C3]CH2N and 2H, [C2]CH2N), 1.54 (m, 2H,
CH2CH2CH2), 1.18 (m, 2H, CH2CH2CH2). 13C{1H} NMR (C6D6,
75.5 MHz, 296 K): δ (ppm) 145.3 (i-PhSZr), 133.3 (PhSZr), 132.7
(Ph), 131.5 (i-PhCH2N), 127.9 (Ph), 127.6 (Ph), 123.4 (Ph), 56.6
(PhCH2N), 55.7 ([C3]CH2N), 55.4 ([C3]CH2N), 53.1 ([C2]CH2N),
49.9 ([C2]CH2N), 24.5 (CH2CH2CH2).
(Bn2Cyclam)Zr(NHPh)2 (20). In a J-Young NMR tube, aniline (12
mg, 0.13 mmol) was added to a C6D6 solution of 16 (30 mg, 0.064
mmol). Full conversion was observed by NMR after 15 min. 1H NMR
(C6D6, 300.1 MHz, 296 K): δ (ppm) 7.23 (m, 4H, m-PhNHZr), 7.16−
6.99 (overlapping, 10H total, 4H, o-PhNHZr, 2H, p-PhCH2N and 4H,
m-PhCH2N or o-PhCH2N), 6.81 (m, 4H, m-PhCH2N or o-PhCH2N),
6.72 (t, 3JH−H = 7 Hz, 2H, p-PhNHZr), 6.09 (s, 2H, PhNHZr), 4.25 (d,
((CHC(Me)CH2)2Cyclam)Zr (15). (MeAll2Cyclam)ZrCl2 (800 mg,
1.71 mmol) and 1.25 mL of a MgClMe solution (3.0 M in THF) were
reacted using the procedure described for the synthesis of 14, affording
a beige solid in 78% yield (526 mg, 1.33 mmol). Crystalline material
suitable for single crystal X-ray diffraction was obtained from a
1
concentrated toluene solution at −20 °C. H NMR (Tol-d8, 300.1
4
MHz, 296 K): δ (ppm) 7.42 (d, JH−H = 1 Hz, 2H, NCH2C(Me)
CHZr), 3.31−3.13 (overlapping, 8H total, 2H, NCH2C(Me)CHZr,
2H, [C3]CH2N and 4H, [C2]CH2N), 3.02 (m, JA‑B = 17 Hz, 2H,
NCH2C(Me)CHZr), 2.92 (m, 2H, [C2]CH2N), 2.76−2.63 (over-
lapping, 4H total, [C3]CH2N), 2.39 (m, 2H, [C2]CH2N), 2.22 (m, 2H,
[C3]CH2N), 1.86 (d, 4JH−H = 1 Hz, 6H, NCH2C(Me)CHZr), 1.77
(m, 2H, CH2CH2CH2), 1.59 (m, 2H, CH2CH2CH2). 13C{1H} NMR
(Tol-d8, 75.5 MHz, 296 K): δ (ppm) 185.0 (NCH2C(Me)CHZr),
150.7 (NCH2C(Me)CHZr), 69.8 (NCH2C(Me)CHZr), 61.0
([C2]CH2N), 56.8 ([C2]CH2N), 55.4 ([C3]CH2N), 54.8 ([C3]
CH2N), 27.4 (CH2CH2CH2), 24.3 (NCH2C(Me)CHZr). Anal.
Calcd for C18H32N4Zr: C, 54.64; H, 8.15; N, 14.16. Found: C, 54.25; H,
8.04; N, 14.10.
J
A‑B = 14 Hz, 2H, PhCH2N), 4.12 (d, JA‑B = 14 Hz, 2H, PhCH2N), 3.69
(m, 2H, [C3]CH2N), 3.55 (m, 2H, [C2]CH2N), 2.91−2.84 (over-
lapping, 6H total, 2H, [C3]CH2N and 4H, 2x[C2]CH2N), 2.79 (m,
2H, [C3]CH2N), 2.37−2.26 (overlapping, 4H total, 2H, [C3]CH2N
and 2H, [C2]CH2N), 1.64 (m, 2H, CH2CH2CH2), 1.36 (m, 2H,
CH2CH2CH2). 13C{1H} NMR (C6D6, 75.5 MHz, 296 K): δ (ppm)
156.0 (i-Ph), 133.0 (m-PhCH2N or o-PhCH2N), 131.8 (i-Ph), 129.7
(m-PhNHZr), 128.6 (overlapping, p-PhCH2N and m-PhCH2N or o-
PhCH2N), 119.2 (o-PhNHZr), 116.7 (p-PhNHZr), 56.9 ([C3]CH2N),
55.7 (PhCH2N), 55.0 ([C2]CH2N), 54.8 ([C3]CH2N), 51.7 ([C2]
CH2N), 27.2 (CH2CH2CH2).
(Bn2Cyclam)Zr(NHNCPh2)2 (21). In a J-Young NMR tube,
benzophenone hydrazone (33 mg, 0.17 mmol) was added to a C6D6
solution of 16 (40 mg, 0.086 mmol). Full conversion was observed by
NMR after 15 min. Crystalline material suitable for single crystal X-ray
diffraction were obtained in the NMR tube solution. 1H NMR (C6D6,
300.1 MHz, 296 K): δ (ppm) 7.96−6.56 (overlapping, 30H, Ph), 4.13
(d, JA‑B = 14 Hz, 2H, PhCH2N), 4.03 (d, JA‑B = 14 Hz, 2H, PhCH2N),
3.35 (m, 2H, [C2]CH2N), 2.99 (m, 2H, [C3]CH2N), 2.50 (m, 2H,
[C2]CH2N), 2.28−2.19 (overlapping, 4H total, 2H, [C3]CH2N and
2H, CH2CH2CH2), 2.12 (m, 2H, [C2]CH2N), 1.93 (m, 2H,
[C3]CH2N), 1.83 (m, 2H, [C3]CH2N), 1.71 (m, 2H, [C2]CH2N),
1.16 (m, 2H, CH2CH2CH2). 13C{1H} NMR (C6D6, 75.5 MHz, 296 K):
δ (ppm) 143.6 (NCPh2), 136.8 (i-Ph), 136.0 (i-Ph), 133.3 (i-Ph), 132.8
(Ph), 132.2 (Ph), 131.2 (Ph), 129.6 (Ph), 129.3 (Ph), 127.0 (Ph), 125.7
(Ph), 125.4 (Ph), 123.1 (Ph), 57.0 (PhCH2N), 54.0 ([C2]CH2N), 53.3
([C3]CH2N), 50.3 ([C3]CH2N), 47.6 ([C2]CH2N), 24.7
(CH2CH2CH2).
(Bn2Cyclam)Zr(OtBu)2 (17). Method A: In a J-Young NMR tube, tert-
butanol (4.4 mg, 0.059 mmol) was added to a C6D6 solution of 16 (14
mg, 0.030 mmol). Full conversion was observed by NMR after 24 h.
Method B: A THF solution of LiOtBu (266 mg, 3.32 mmol) was added
to a suspension of (Bn2Cyclam)ZrCl2 (900 mg, 1.66 mmol) in the same
solvent. The mixture was refluxed overnight. The solvent was
evaporated, and the product was extracted with small volumes of
warm toluene. Evaporation to dryness afforded a white solid in 69%
yield (0.71 g, 1.15 mmol). Crystalline material suitable for X-ray
diffraction was obtained from a concentrated toluene solution at −20
°C. 1H NMR (C6D6, 300.1 MHz, 296 K): δ (ppm) 7.37−7.00
(overlapping, 10H total, PhCH2N), 4.57 (d, JA‑B = 14 Hz, 2H,
PhCH2N), 4.37−4.32 (overlapping, 4H total, JA‑B = 14 Hz, 2H,
PhCH2N and 2H, [C3]CH2N), 3.60 (m, 2H, [C2]CH2N), 3.43 (m,
2H, [C3]CH2N), 2.96 (m, 2H, [C3]CH2N), 2.84 (m, 4H, 2x[C2]-
CH2N), 2.35 (m, 2H, [C3]CH2N), 2.19 (m, 2H, [C2]CH2N), 1.74−
1.63 (overlapping, 20H total, 18H, C(CH3)3 and 2H, CH2CH2CH2),
1.15 (d, 2H, CH2CH2CH2). 1H NMR (toluene-d8, 300.1 MHz, 253 K):
δ (ppm) 7.25−7.13 (overlapping, 10H total, PhCH2N), 4.56 (d, 2JH−H
= 14 Hz, 2H, PhCH2N), 4.39−4.30 (overlapping, 4H total, 2JH−H = 14
Hz, 2H, PhCH2N and 2H, [C3]CH2N), 3.58 (m, 2H, [C2]CH2N),
3.43 (m, 2H, [C3]CH2N), 2.97 (m, 2H, [C3]CH2N), 2.79 (m, 4H,
2x[C2]CH2N), 2.31 (m, 2H, [C3]CH2N), 2.11 (m, 2H, [C2]CH2N),
1.86−1.72 (overlapping, 20H total, 18H, C(CH3)3 and 2H,
CH2CH2CH2), 1.16 (m, 2H, CH2CH2CH2). 13C{1H} NMR
(toluene-d8, 75.5 MHz, 253 K): δ (ppm) 133.7 (i-PhCH2N), 132.7
(PhCH2N), 128.0 (overlapping, 2xPhCH2N), 74.3 (C(CH3)3), 56.0
(PhCH2N), 55.7 (overlapping, 2x[C3]CH2N), 52.0 ([C2]CH2N), 48.1
([C2]CH2N), 34.6 (C(CH3)3), 24.3 (CH2CH2CH2). Anal. Calcd for
C32H52N4O2Zr: C, 62.39; H, 8.51; N, 9.10. Found: C, 62.10; H, 8.78;
N, 8.73.
(Bn2Cyclam)Zr(C3H3N2)2 (22). In a J-Young NMR tube, pyrazole (12
mg, 0.18 mmol) was added to C6D6 solution of 16 (40 mg, 0.085
mmol). Full conversion was observed by NMR after 15 min. Crystalline
material suitable for single crystal X-ray diffraction were obtained in the
1
NMR tube solution. H NMR (C6D6, 300.1 MHz, 296 K): δ (ppm)
(Bn2Cyclam)Zr(OPh)2 (18). In a J-Young NMR tube, phenol (18 mg,
0.19 mmol) was added to a C6D6 solution of 16 (44 mg, 0.094 mmol).
Full conversion was observed by NMR after 15 min. 1H NMR (C6D6,
7.85 (d, 2JH−H = 2 Hz, 4H, NCHCH), 7.22−6.95 (overlapping, 10H,
2
PhCH2N), 6.62 (t, JH−H = 2 Hz, 2H, NCHCH), 4.48 (m, 2H,
3
[C3]CH2N), 4.01 (d, JA‑B = 14 Hz, 2H, PhCH2N), 3.63 (m, 2H,
[C3]CH2N), 3.46 (d, JA‑B = 14 Hz, 2H, PhCH2N), 3.45−3.19
(overlapping, 6H total, 3x[C2]CH2N), 3.06 (m, 2H, [C2]CH2N), 2.94
(m, 2H, [C3]CH2N), 2.60 (m, 2H, [C3]CH2N), 1.67 (m, 2H,
CH2CH2CH2), 1.07 (m, 2H, CH2CH2CH2). 13C{1H} NMR (C6D6,
75.5 MHz, 296 K): δ (ppm) 134.7 (NCHCH), 133.8 (i-PhCH2N),
132.1 (PhCH2N), 127.7 (PhCH2N), 127.1 (PhCH2N), 111.5
300.1 MHz, 296 K): δ (ppm) 7.23 (t, JH−H = 9 Hz, 4H, m-PhOZr)
7.10−7.06 (overlapping, 14H total, 10H, PhCH2N and 4H, o-PhOZr),
3
6.80 (t, JH−H = 9 Hz, 2H, p-PhOZr), 4.44 (d, JA‑B = 14 Hz, 2H,
PhCH2N), 4.34 (d, JA‑B = 14 Hz, 2H, PhCH2N), 4.23 (m, 2H,
[C3]CH2N), 3.56 (m, 2H, [C2]CH2N), 3.14 (m, 2H, [C3]CH2N),
2.93−2.76 (overlapping, 6H total, 4H, 2x[C2]CH2N and 2H,
[C3]CH2N), 2.34 (m, 2H, [C3]CH2N), 2.17 (m, 2H, [C2]CH2N),
H
Inorg. Chem. XXXX, XXX, XXX−XXX