Heterobimetallic Samarium(III) and Titanium(IV) Complexes with Bifunctional Catalytic Properties

Zhou, Fengying; Lin, Miaoshui; Li, Lei; Zhang, Xueqing; Zhou, C.; Li, Yahong; Zhao, Yang; Wu, Jung-Lin; Qian, Guimin; Hu, Bin; Li, Wu

doi:10.1021/om1010935

Cited by 19 publications

(10 citation statements)

References 54 publications

(18 reference statements)

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“…However, the presence of two sets of Sm–N imin distances [2.698–2.884 Å and 2.913–2.977 Å] clearly represents the asymmetric arrangement of the bis‐iminopyrrolyl moieties towards the samarium ion, due to the bulky size of the ligand backbone. It is noted that a similar asymmetric arrangement of the bis‐iminopyrrolyl moieties was reported in the related samarium complex [(C 4 H 4 N) 9 Sm]‐[Sm(NH 3 ) 9 ], [Sm(Hbptd)(H 2 bptd)] (H 3 bptd = 1,9‐bis(2‐pyrrolyl)‐2,5,8‐triazanona‐1,8‐diene, and yttrium complex [{Y(ArN=CH} 2 C 4 H 2 N)} 3 ] (Ar = C 6 H 4 ‐OMe‐ p , C 6 H 4 ‐Me‐ p ), reported by Mashima et al…”

Section: Resultssupporting

confidence: 59%

Synthesis and Structure of Unprecedented Samarium Complex with Bulky Bis‐iminopyrrolyl Ligand via Intramolecular C=N Bond Activation

Das

Anga

Harinath

et al. 2017

Zeitschrift anorg allge chemie

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An unprecedentate samarium complex of the molecular composition [{κ 3 -{(Ph 2 CH)N=CH} 2 C 4 H 2 N)}{κ 3 -{(Ph 2 CHN=CH)(Ph 2 CHNCH)C 4 H 2 N}Sm} 2 ] (2), which was isolated by the reaction of a potassium salt of 2,5-bis{N-(diphenylmethyl)-iminomethyl}pyrrolyl ligand [K(THF) 2 {(Ph 2 CH)N=CH} 2 C 4 H 2 N)] (1) with anhydrous samarium diiodide in THF at 60°C through the in situ reduction of imine bond is presented. The homoleptic samarium complex [[κ 3 -{(Ph 2 CH)-N=CH} 2 C 4 H 2 N)] 3 Sm] (3) can also be obtained from the reaction of compound 1 with anhydrous samarium * Dr. T. K. Panda E-Mail: tpanda@iith.ac.in [a]

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Section: Resultssupporting

confidence: 59%

Synthesis and Structure of Unprecedented Samarium Complex with Bulky Bis‐iminopyrrolyl Ligand via Intramolecular C=N Bond Activation

Das

Anga

Harinath

et al. 2017

Zeitschrift anorg allge chemie

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“…[29][30][31] Hydrated thorium(IV) predominates in strongly acidic aqueous solution, with hydrolysis occurring as pH increases. [27] Thorium(IV) is nine-coordinate in solid nonakis(κO-dimethyl sulfoxide)thorium(IV) perchlorate, [Th(dmso) 9 ](ClO 4 ) 4 , in which nine dmso oxygen atoms form a distorted tricapped trigonal prism with a mean Th-O bond length of 2.455 Å. [32] A nine-coordinate thorium solvate with eight dmso molecules and one chloride ion has been reported as well.…”

Section: +mentioning

confidence: 98%

“…[1][2][3] The properties and characteristics exhibited, such as reactivity, color, and complex formation ability sometimes vary profoundly depending on the solvent used. [4][5][6][7][8][9] Dimethyl sulfoxide (dmso) is an important polar aprotic solvent that dissolves both polar and nonpolar compounds well and is fully miscible with water as well as many organic solvents. [10] It is also capable of solvating both soft and hard metal ions well, thereby making dmso frequently used as solvent or cosolvent for chemical reactions that involving metal salts as, for example, Finkelstein reactions and nucleophilic substitutions.…”

Section: Introductionmentioning

confidence: 99%

A Coordination Chemistry Study of Solvated Thorium(IV) Ions in Two Oxygen‐Donor Solvents

2011

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The structures of the dimethyl sulfoxide (dmso) and N,N′‐dimethylpropyleneurea (dmpu) solvated thorium(IV) ions have been studied in solution by extended X‐ray absorption fine structure (EXAFS), and the structure of the solid oxonium bis[nonakis(κO‐dimethyl sulfoxide)]thorium(IV) trifluoromethanesulfonate dihydrate, (H3O)[Th((CH3)2SO)9]2(CF3SO3)9·2H2O (1) has been determined by single‐crystal X‐ray diffraction and EXAFS. Compound 1 was crystallized by evaporating a saturated dmso solution. It consists of two individual nonakis(κO‐dimethyl sulfoxide)thorium(IV) units, both of which have a tricapped trigonal prismatic configuration, as also found in nonakis(dimethyl sulfoxide)thorium(IV) perchlorate previously reported. Mean Th–O bond lengths of 2.47 and 2.43 Å are found for the two structural units, respectively, for which the differences may be explained by differences in occupancy and temperature factors. The EXAFS data of 1 revealed mean Th–O and S–O bond lengths of 2.449(3) and 1.525(3) Å, respectively, and a Th–O–S bond angle of 135.2(5)° to give a Th···S distance of 3.665(7) Å. In dmso solution, the mean Th–O and S–O bond lengths are 2.447(3) and 1.534(3) Å, respectively, the Th–O–S bond angle is 133.5(5)°, and there is a Th···S distance of 3.672(7) Å. The Th–O bond‐length distribution is somewhat asymmetric in both samples with Rmax values of 2.424 and 2.422 Å for 1 and solution, respectively. In dmpu solution, the Th–O and C–O bond lengths are 2.404(5) and 1.264(2) Å, respectively, and there is a Th–O–C angle of 157.1(5)° to give a Th···C distance of 3.594(7) Å. The observed Th–O bond length indicates strongly that thorium(IV) is eight‐coordinate in dmpu.

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“…In our previous work, we have chosen pyrrole as an ancillary ligand to tune the activity of the complexes in the catalytic studies. Employing pyrrole as an ancillary ligand has always been a hot pot for chemists, due to a couple of considerations .…”

Section: Introductionmentioning

confidence: 99%

Group 4 Complexes Bearing Pyrrolide Ligand for Intramolecular Alkene Hydroamination and Activation of C≡N Bond

Jiang

Wang

Liu

et al. 2018

Zeitschrift anorg allge chemie

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Titanium and zirconium complexes supported by a pyrrolide ligand HL 1 [HL 1 = 2-cyano-1H-pyrrole], Ti 2 (L 2 ) 2 (NMe 2 ) 2 (1) and Zr 3 (L 2 ) 3 (NMe 2 ) 6 (2) [L 2 = N,N-dimethyl-1H-pyrrol-2-carboximidamide, NMe 2 -L 1 ] were synthesized and characterized. The ligand L 2 was generated by activation of CϵN bond of HL 1 with HNMe 2 . In complex 1, two Ti IV atoms are bridged by two nitrogen atoms. There

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Heterobimetallic Samarium(III) and Titanium(IV) Complexes with Bifunctional Catalytic Properties

Cited by 19 publications

References 54 publications

Synthesis and Structure of Unprecedented Samarium Complex with Bulky Bis‐iminopyrrolyl Ligand via Intramolecular C=N Bond Activation

Synthesis and Structure of Unprecedented Samarium Complex with Bulky Bis‐iminopyrrolyl Ligand via Intramolecular C=N Bond Activation

A Coordination Chemistry Study of Solvated Thorium(IV) Ions in Two Oxygen‐Donor Solvents

Group 4 Complexes Bearing Pyrrolide Ligand for Intramolecular Alkene Hydroamination and Activation of C≡N Bond

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