Group 1 and group 2 metal complexes supported by a bidentate bulky iminopyrrolyl ligand: synthesis, structural diversity, and ε-caprolactone polymerization study

• Published in: Dalton transactions : an international journal of inorganic chemistry 2015-01, Vol.44 (46), p.19865-19879
• Main Authors: Kottalanka, Ravi K, Harinath, A, Rej, Supriya, Panda, Tarun K
• Format: Article
• Language: English
• Subjects: Alkaline earth metals; Alkanes; Caproates - chemical synthesis; Caproates - chemistry; Coordination Complexes - chemical synthesis; Coordination Complexes - chemistry; Coordination compounds; Decomposition reactions; Imines - chemical synthesis; Imines - chemistry; Lactones - chemical synthesis; Lactones - chemistry; Ligands; Magnesium; Metals, Alkaline Earth - chemical synthesis; Metals, Alkaline Earth - chemistry; Metathesis; Models, Molecular; Polymerization; Pyrroles - chemical synthesis; Pyrroles - chemistry; Strontium
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c5dt03222a

We report here a series of alkali and alkaline earth metal complexes, each with a bulky iminopyrrolyl ligand [2-(Ph3CN=CH)C4H3NH] (1-H) moiety in their coordination sphere, synthesized using either alkane elimination or silylamine elimination methods or the salt metathesis route. The lithium salt of molecular composition [Li(2-(Ph3CN=CH)C4H3N)(THF)2] (2) was prepared using the alkane elimination method, and the silylamine elimination method was used to synthesize the dimeric sodium and tetra-nuclear potassium salts of composition [(2-(Ph3CN=CH)C4H3N)Na(THF)]2 (3) and [(2-(Ph3CN=CH)C4H3N)K(THF)0.5]4 (4) respectively. The magnesium complex of composition [(THF)2Mg(CH2Ph){2-(Ph3CN=CH)C4H3N}] (5) was synthesized through the alkane elimination method, in which [Mg(CH2Ph)2(OEt2)2] was treated with the bulky iminopyrrole ligand 1-H in 1 : 1 molar ratio, whereas the bis(iminopyrrolyl)magnesium complex [(THF)2Mg{2-(Ph3CN=CH)C4H3N}2] (6) was isolated using the salt metathesis route. The heavier alkaline earth metal complexes of the general formula {(THF)nM(2-(Ph3CN=CH)C4H3N)2} [M = Ca (7), Sr (8), and n = 2; M = Ba (9), n = 3] were prepared in pure form using two synthetic methods: in the first method, the bulky iminopyrrole ligand 1-H was directly treated with the alkaline earth metal precursor [M{N(SiMe3)2}2(THF)n] (where M = Ca, Sr and Ba) in 2 : 1 molar ratio in THF solvent at ambient temperature. The complexes 7-9 were also obtained using the salt metathesis reaction, which involves the treatment of the potassium salt (4) with the corresponding metal diiodides MI2 (M = Ca, Sr and Ba) in 2 : 1 molar ratio in THF solvent. The molecular structures of all the metal complexes (1-H, 2-9) in the solid state were established through single-crystal X-ray diffraction analysis. The complexes 5-9 were tested as catalysts for the ring-opening polymerization of ε-caprolactone. High activity was observed in the heavier alkaline earth metal complexes 7-9, with a very narrow polydispersity index in comparison to that of magnesium complexes 5 and 6.