≡
Preparation of [Nd(H-TMG)2(4MeDBP)2{O(CH2)3C CH}] (3)
Experimental
≡
and [La(H-TMG)2(DBP)2{O(CH2)3C CH}] (4)
All compounds were handled with rigorous exclusion of air and
water using standard glove box techniques. All anhydrous solvents
were stored under argon and used as received in sure-seal bottles.
H-TMG, H-DBP, H-4MeDBP, ethanol, and 4-pentyn-1-ol were
used as received from commercial suppliers. La[N{Si(CH3)3}2]3
and Nd[N{Si(CH3)3}2]3 were synthesized according to literature
procedures.32 FT-IR data was obtained on a Bruker Tensor 27
instrument using KBr pellets under an atmosphere of flowing
nitrogen. Melting points were determined on samples in sealed
capillary tubes under an atmosphere of argon using an Elec-
trothermal Mel-Temp apparatus and are uncorrected. Elemental
analysis was performed on a Perkin-Elmer 2400 Series 2 CHN-
[Ln(H-TMG)2(OAr)2(OEt)] (Ln = Nd, La) was dissolved in a
1 : 1 hexanes : THF mixture. To this solution, 4-pentyn-1-ol,
dissolved in hexanes, was added dropwise. The resultant clear
solution was stirred for 10 min. This solution was then set out
to evaporate overnight. After evaporation, blue crystals of 3 and
colorless crystals of 4 formed.
≡
[Nd(H-TMG)2(4MeDBP)2{O(CH2)3C CH}]
(3). [Nd(H-
TMG)2(4MeDBP)2(OEt)] (240 mg, 0.28 mmol) and 4-pentyn-1-ol
(23 mg, 0.28 mmol) were used. Yield 54% (130 mg, 0.15 mmol).
Found: C 60.70, H 8.96, N 8.28%. C45H79N6NdO3 requires: C
60.30, H 8.88, N 9.38%. Mp = 146 ◦C. umax(KBr)/cm-1 3643 (m),
3318 (m), 2956 (s), 2706 (w), 2119 (w), 1752 (w), 1590 (s),
1518 (m), 1415 (s), 1261 (s), 1119 (s), 1063 (m), 1026 (w), 921 (w),
898 (w), 863 (m), 819 (m), 802 (m), 776 (w), 626 (w), 576 (w),
556 (w), 541 (w), 507 (m).
S/O Elemental Analyzer. All solution H and 13C{ H} spectra
were obtained with a Bruker DRX 400 spectrometer at 400 and
100 MHz, respectively.
1
1
Preparation of [Nd(H-TMG)2(4MeDBP)2(OEt)] (1) and
[La(H-TMG)2(DBP)2(OEt)] (2)
≡
[La(H-TMG)2(DBP)2{O(CH2)3C CH}] (4). La(H-TMG)2-
(DBP)2(OEt) (180 mg, 0.22 mmol) and 4-pentyn-1-ol (18 mg,
0.21 mmol) were used. Yield 59% (110 mg, 0.13 mmol) formed.
Found: C 58.98, H 8.20, N 8.52. C43H72LaN6O3 requires: C
59.84, H 8.76, N 9.74%. Mp = 152 ◦C. umax(KBr)/cm-1 3640 (w),
3335 (w), 3300 (m), 3071 (w), 2951 (s), 2704 (w), 2532 (w),
2116 (w), 1587 (s), 1566 (s), 1529 (m), 1467 (m), 1425 (s), 1403 (s),
1382 (s), 1257 (s), 1200 (m), 1102 (s), 1062 (m), 1026 (s), 960 (w),
924 (w), 899 (w), 884 (w), 859 (m), 817 (m), 750 (s), 701 (w),
Ln[N{Si(CH3)3}2]3 (Ln = Nd, La), HOAr (OAr = 4MeDBP,
DBP), H-TMG, and ethanol were dissolved in hexanes separately.
The HOAr, H-TMG, and ethanol were mixed together in one
vial and then added dropwise to the stirring Ln[N{Si(CH3)3}2]3
solution. A precipitate formed which upon addition of THF
was dissolved. The resulting solution was then stirred for 5 min
and left to evaporate overnight. After evaporation of the volatile
components, blue crystals of 1 and colorless crystals of 2 were
isolated.
1
640 (m), 591 (w), 557 (w), 537 (w), 483 (w), 444 (w). H-NMR
(C6D6): d = 7.27 (s, 4 H, OC6H3((C(CH3)3)2-2,6), 6.96 (t, 2 H,
=
OC6H3((C(CH3)3)2-2,6), 3.49 (s, 2 H, HN C(N((CH3)2)2), 2.60
=
(s, 24 H, HN C(N((CH3)2)2), 2.16 (t, 2 H, OCH2CH2CH2CCH),
[Nd(H-TMG)2(4MeDBP)2(OEt)]
(1). Nd[N{Si(CH3)3}2]3
1.85 (s,
1
H, OCH2CH2CH2CCH), 1.47 (s, 36 H,
(200 mg, 0.32 mmol), H-4MeDBP (142 mg, 0.64 mmol), H-TMG
(74 mg, 0.64 mmol) and HOEt (15 mg, 0.32 mmol) were used.
Yield 78% (220 mg, 0.26 mmol) Found: C 59.07, H 8.61, N 8.39%.
C42H77N6NdO3 requires: C 58.77, H 9.04, N 9.79%. Mp = 156 ◦C.
OC6H3((C(CH3)3)2-2,6), 1.08 (t, 2 H, OCH2CH2CH2CCH),
0.99 (m, 2 H, OCH2CH2CH2CCH) ppm. 13C{ H} NMR
1
=
(C6D6): d = 165.8 (HN C(N((CH3)2)2), 137.9, 135.7, 125.0,
114.3 (OC6H3((C(CH3)3)2-2,6), 38.9 (OCH2CH2CH2CCH),
u
max(KBr)/cm-1 3650 (w), 3312 (w), 2954 (s), 1591 (s), 1425 (s),
=
38.4 (OCH2CH2CH2CCH), 35.2 (HN C(N((CH3)2)2), 34.1
1260 (m), 1119 (m), 1062 (w), 898 (w), 862 (m), 819 (m), 802 (m),
775 (w), 708 (w), 576 (w), 509 (w), 488 (w), 435 (w).
(OCH2CH2CH2CCH), 31.6 (OC6H3((C(CH3)3)2-2,6), 30.2
(OC6H3((C(CH3)3)2-2,6), 22.8 (OCH2CH2CH2CCH), 14.2
(OCH2CH2CH2CCH) ppm.
[La(H-TMG)2(DBP)2(OEt)] (2). La[N{Si(CH3)3}2]3 (200 mg,
0.32 mmol), H-DBP (114 mg, 0.65 mmol), H-TMG (74 mg,
0.64 mmol) and HOEt (15 mg, 0.32 mmol) were used. Yield
66% (180 mg, 0.22 mmol) formed. Found: C 57.30, H 8.79,
N 9.69%. C45H79N6LaO3 requires: C 58.24, H 8.92, N 10.19%.
Mp = 126 ◦C. umax(KBr)/cm-1 3334 (w), 3070 (w), 2951 (s),
2696 (w), 2527 (w), 2180 (w), 1839 (w), 1567 (s), 1530 (s),
1461 (m), 1404 (s), 1381 (m), 1257 (s), 1199 (m), 1127 (m),
1062 (m), 937 (w), 900 (m), 883 (w), 858 (m), 816 (m),
Preparation of [Nd(4MeDBP)3(H-TMG)] (5) and
[La(DBP)3(H-TMG)] (6)
Ln[N{Si(CH3)3}2]3 (Ln = Nd, La), HOAr (H-4MeDBP, H-DBP)
and H-TMG were each dissolved in hexanes. HOAr and H-
TMG were mixed together in one vial and added dropwise to
the Ln[N{Si(CH3)3}2]3 solution. A precipitate formed and was
dissolved with THF. Blue crystals of 5 and colorless crystals of 6
were formed after slow evaporation of the respective solutions.
1
749 (m), 640 (m), 557 (w), 537 (w), 484 (w), 442 (w). H-NMR
(C6D6): d = 7.60 (s, 4 H, OC6H3((C(CH3)3)2-2,6), 6.95 (t, 2 H,
=
OC6H3((C(CH3)3)2-2,6), 5.48 (s, 2 H, HN C(N((CH3)2)2), 4.47
[Nd(4MeDBP)3(H-TMG)] (5). Nd[N{Si(CH3)3}2]3 (200 mg,
0.32 mmol), H-4MeDBP (212 mg, 0.96 mmol) and H-TMG
(37 mg, 0.32 mmol) were used. Yield 37% (106 mg, 0.12 mmol).
Found: C 64.16, H 8.94, N 3.87%. C50H82N3NdO3 requires: C
65.46, H 9.01, N 4.58%. Mp = 137 ◦C. umax(KBr)/cm-1 3324 (w),
2955 (w), 2916 (m), 2280 (w), 1754 (w), 1710 (w), 1690 (w),
1657 (w), 1563 (m), 1536 (m), 1416 (s), 1384 (w), 1355 (w), 1233 (s),
=
(q, 2 H, OCH2CH3), 2.69, 2.13 (s, 12 H, HN C(N((CH3)2)2), 1.90
(s, 36 H, OC6H3((C(CH3)3)2-2,6), 1.58 (t, 3 H, OCH2CH3) ppm.
13
1
=
C{ H} NMR (C6D6): d = 165.8 (HN C(N((CH3)2)2), 138.1,
127.2, 124.9, 114.4 (OC6H3((C(CH3)3)2-2,6), 39.0 (OCH2CH3),
=
38.4 (OC6H3((C(CH3)3)2-2,6), 35.1 (HN C(N((CH3)2)2), 31.4
(OC6H3((C(CH3)3)2-2,6), 14.2 (OCH2CH3) ppm.
10606 | Dalton Trans., 2009, 10601–10608
This journal is
The Royal Society of Chemistry 2009
©