Chromium Diamino-bis(phenolate) Complexes as Catalysts for the Ring-Opening Copolymerization of Cyclohexene Oxide and Carbon Dioxide,Inorganic Chemistry

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Chromium Diamino-bis(phenolate) Complexes as Catalysts for the Ring-Opening Copolymerization of Cyclohexene Oxide and Carbon Dioxide
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-10-04 , DOI: 10.1021/acs.inorgchem.0c02348
Kenson Ambrose ₁ , Jennifer N. Murphy ₁ , Christopher M. Kozak ₁

Affiliation

Chromium diamino-bis(phenolate) complexes, CrXL [where L = 6,6′-((1,4-diazepane-1,4-diyl)bis(methylene))bis(2,4-dimethylphenolato) and X = Cl^– (1), OH^– (2), and N₃^– (3)], were prepared and characterized by MALDI-TOF MS and single-crystal X-ray diffraction. Complex 1 crystallized as two linkage isomers, specifically a green chloride-bridged dimer (1) and a pink asymmetrically bridged isomer exhibiting one chloride bridging atom and one bridging phenolate oxygen (1′). Adventitious moisture during sample handling causes the formation of hydroxide-containing complex 2. The reaction of 1 with PPNN₃ (where PPN = bis(triphenylphosphine)iminium) permits the isolation of a crystalline chromium azide complex, 3, which was structurally authenticated. Complex 1 showed good activity toward the ring-opening copolymerization of cyclohexene oxide and carbon dioxide with an added chloride, azide, or 4-(dimethylamino)pyridine (DMAP) cocatalyst to give a completely alternating polycarbonate with a narrow molecular weight dispersity.

中文翻译：

铬二氨基双（酚盐）配合物作为环己烯氧化物和二氧化碳开环共聚合的催化剂

铬二氨基-双（酚盐）配合物，CrX L [其中L = 6,6'-（（（1,4-二氮杂-1,4-二基）双（亚甲基））双（2,4-二甲基苯酚），X =氯^-（1），OH ^-（2）和N ₃^-（3）]，制备和表征通过MALDI-TOF MS和单晶X射线衍射。配合物1结晶为两种键合异构体，特别是绿色的氯桥联二聚体（1）和粉红色的不对称桥联异构体，具有一个氯桥连原子和一个桥连酚盐氧（1'）。样品处理过程中不定的水分会导致形成含氢氧化物的络合物2。1与PPNN ₃的反应（其中PPN =双（三苯基膦）亚胺）可分离出结晶的叠氮化铬络合物3，该络合物在结构上已得到验证。配合物1对环己烯氧化物和二氧化碳与添加的氯化物，叠氮化物或4-（二甲基氨基）吡啶（DMAP）助催化剂的开环共聚表现出良好的活性，从而得到分子量分布窄的完全交替的聚碳酸酯。

更新日期：2020-10-21

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