Synthesis， Characterization and Catalytic Activity of Benzylamine⁃bridged Bis（phenolato）lanthanide Complexes

doi:10.19894/j.issn.1000-0518.210482

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (5): 843-851.DOI: 10.19894/j.issn.1000-0518.210482

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Synthesis， Characterization and Catalytic Activity of Benzylamine⁃bridged Bis（phenolato）lanthanide Complexes

Hong-Xia CHEN¹^,²^,³, Bao-Xia LI¹, Ying-Ming YAO¹(), Peng LIU⁴

^1.College of Chemistry，Chemical Engineering and Materials Science，Soochow University，Suzhou 215123，China
^2.Jiangsu Canlon Building Materials Co. ，Ltd，Suzhou 215234，China
^3.Department of Laboratory and Equipment Management，Soochow University，Suzhou 215021，China
^4.Testing and Analysis Center，Soochow University，Suzhou 215123，China

Received:2021-09-28 Accepted:2022-01-04 Published:2022-05-01 Online:2022-05-24
Contact: Ying-Ming YAO
About author:yaoym@suda.edu.cn
Supported by:
the National Natural Science Foundation of China(21674070)

Abstract

Abstract:

Lanthanide metal complexes stabilized by benzylamine-bridged bis（phenolato） ligand，（PhN｛CH₂-（2-O-C₆H₂-Bu $2 t$ -3，5）｝₂）（L¹）， were synthesized by the reaction of the ligand precursor L¹H₂ with lanthanide amide. The reaction media has profound influence on the reaction. The reaction of Ln［N（SiMe₃）₂］₃（μ-Cl）Li（THF）₃ with L¹H₂ in a 1∶1 molar ratio is performed in toluene at 90 ℃ to give the desired benzylamine-bridged bis（phenolate） lanthanide amido complexes L¹LnN（SiMe₃）₂（THF）（Ln = Yb （1）， Sm （2））， while the same reaction of Sm［N（SiMe₃）₂］₃（μ-Cl）Li（THF）₃with L¹H₂ in a 1∶1 molar ratio in THF at 50 ℃ only gives the unexpected Sm-Li heterobimetallic complex （THF）LiL¹₂Sm （3）. All of these complexes were characterized by IR， elemental analysis and single crystal X-ray diffraction. The catalytic activities of complexes 1 and 2 for the ring-opening polymerization of L-lactide and D，L-lactide were tested. It is found that these complexes are efficient initiators for lactide polymerization to give polylactide with high relative molecular mass. Complex 1 has good stereoselectivity for D，L-lactide polymerization to give syndio-rich polylactide （P_r=0.87）.

Key words: Benzylamine-bridged bis（phenolato） ligand, Lanthanide complex, Lactide, Polymerization

CLC Number:

O633

Hong-Xia CHEN, Bao-Xia LI, Ying-Ming YAO, Peng LIU. Synthesis， Characterization and Catalytic Activity of Benzylamine⁃bridged Bis（phenolato）lanthanide Complexes[J]. Chinese Journal of Applied Chemistry, 2022, 39(5): 843-851.

Figures/Tables 7

Table 1 Crystallographic data for complexes 1-3

配合物Complex	1	2	3
CCDC Number	2097769	2097770	2121352
分子式Formula	C₄₆H₇₅N₂O₃Si₂Yb	C₄₆H₇₅N₂O₃Si₂Sm	C₉₁H₁₄₁N₂O₅LiSm
重均相对分子质量M_w	933.30	910.61	1500.35
温度T/K	223（2）	223（2）	223（2）
晶系Crystal system	Triclinic	Monoclinic	Monoclinic
空间群Space group	Pī	P2₁/c	P2₁/n
a/nm	1.4700（3）	1.5257（5）	1.5781（3）
b/nm	1.5140（3）	1.4744（4）	2.9112（5）
c/nm	2.1544（3）	2.1691（7）	2.0335（4）
β/（°）	89.712（9）	102.573（8）	105.103（4）
V/nm³	4.682 （14）	4.762（2）	9.019（3）
Z	4	4	4
D_calcd/（g·cm^-3）	1.324	1.270	1.105
μ/mm^-1	2.087	1.321	0.698
F（000）	1948	1916	3224
θ_max/（°）	25.50	25.50	25.50
总衍射点数 Reflections collected	38946	38729	44902
独立衍射点数Unique reflections	17309	8841	16698
参加结构精修的衍射点数Parameters refined	974	476	832
Final R ［I>2.0σ（I）］	0.0496	0.0743	0.1273
wR	0.1211	0.1466	0.2235
GOF on F²	1.068	1.119	1.158

Table 2 Selected bond lengths （nm） and bond angles （°） of complexes 1 and 2

键长/nm Bond lenghths/nm	1	2
Ln1—O1	0.2079（3）	0.2168（4）
Ln1—O2	0.2088（3）	0.2173（4）
Ln1—N2	0.2223（4）	0.2297（5）
Ln1—O3	0.2275（3）	0.2406（4）
Ln1—N1	0.2427（4）	0.2546（4）
键角/（°） Bond angles/（°）	1	2
O1—Ln1—O2	133.10（14）	129.56（15）
O1—Ln1—N2	111.95（14）	113.31（16）
O2—Ln1—N2	114.36（14）	115.54（16）
O1—Ln1—O3	91.07（12）	93.02（15）
O2—Ln1—O3	87.33（12）	87.78（15）
N2—Ln1—O3	100.92（14）	103.09（16）
O1—Ln1—N1	78.15（12）	74.82（14）
O2—Ln1—N1	77.67（12）	75.64（14）
N2—Ln1—N1	112.89（13）	112.74（16）
O3—Ln1—N1	146.16（13）	144.12（14）

Fig.1 Solid state structuer of complex 1 （A）， complex 2 （B） and complex 3 （C）

Table 3 Selected bond lengths （nm） and bond angles （°） of complex 3

键长/nm Bond lenghths/nm
Ln1—O1	0.2194（5）	Ln1—O4	0.2307（5）
Ln1—O3	0.2196（5）	Ln1—N1	0.2686（6）
Ln1—O2	0.2298（5）	Ln1—N2	0.2720（6）
键角/（°） Bond angles/（°）
O1—Ln1—O2	150.05（18）	O4—Ln1—N1	91.57（18）
O1—Ln1—O3	101.11（19）	O1—Ln1—N2	117.03（18）
O3—Ln1—O2	95.10（19）	O3—Ln1—N2	76.74（17）
O1—Ln1—O4	99.85（18）	O2—Ln1—N2	91.04（17）
O3—Ln1—O4	149.36（18）	O4—Ln1—N2	73.90（17）
O2—Ln1—O4	76.99（17）	N1—Ln1—N2	161.73（17）
O1—Ln1—N1	75.72（18）	O2—Li1—O4	99.3（7）
O3—Ln1—N1	115.13（18）	O2—Li1—O5	120.3（8）
O2—Ln1—N1	74.61（17）	O4—Li1—O5	136.0（9）

Table 4 Polymerization of L?lactide initiated by complexes 1， 2a

序号 Entry	引发剂 Initiator	单体/引发剂物质的量比 n（LA）/n（1）	反应时间 Reaction time/h	收率 Yield/% ^b	相对分子质量 10^-4×M_n^c	相对分子质量分布 M_w/M_n^d
1	1	500	4	41	16.19	1.40
2	2	500	2	78	9.94	1.39
3	2	1000	3	81	13.83	1.34
4	2	2000	3	55	14.67	1.31

Table 5 Polymerization of D，L?lactide initiated by complexes 1， 2a

序号 Entry	引发剂 Initiator	单体/引发剂物质量的比 n（LA）/n（I）	反应时间 Reaction time/h	收率 Yield/% ^b	数均相对分子质量 10^-4×M $n c$	相对分子质量分布 M_w/M $n d$	杂同含量 P_r
1	1	250	3	69	5.58	1.31	0.69
2	1	500	3	60	8.06	1.43	0.68
3	2	250	3	84	7.58	1.32	0.84
4	2	500	3	64	7.99	1.44	0.87

Table 5 Polymerization of D，L?lactide initiated by complexes 1， 2a

序号 Entry	引发剂 Initiator	单体/引发剂物质量的比 n（LA）/n（I）	反应时间 Reaction time/h	收率 Yield/% ^b	数均相对分子质量 10^-4×M $n c$	相对分子质量分布 M_w/M $n d$	杂同含量 P_r
1	1	250	3	69	5.58	1.31	0.69
2	1	500	3	60	8.06	1.43	0.68
3	2	250	3	84	7.58	1.32	0.84
4	2	500	3	64	7.99	1.44	0.87

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Synthesis， Characterization and Catalytic Activity of Benzylamine⁃bridged Bis（phenolato）lanthanide Complexes

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