Exploring the Nuclearity and Structural Motifs of Phenoxyimine Alkaline Earth Complexes.

IF 2.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2025-03-03 eCollection Date: 2025-03-24 DOI:10.1021/acs.organomet.4c00504

Amy V Rizzo, Rebecca L Jones, Matthew D Haynes, Clement G Collins Rice, Jean-Charles Buffet, Zoë R Turner, Dermot O'Hare

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Abstract

The nuclearity and structural motifs of alkaline earth complexes supported by bidentate phenoxyimine ligands has been explored by modulation of the stereoelectronic profile of the ligand, the atomic number of the metal, and the synthetic protocol. Changing the size of the N-imine substituents was found to have no effect on protonolysis reactions between [MgN″₂]₂ or CaN″₂(thf)₂ (N″ = N(SiMe₃)₂) and H ^{^t Bu₂,Ar}L (1-OH-2-CH = NAr-4,6- ^t Bu-C₆H₂; Ar = 2,6-ⁱPr-C₆H₃ = Dipp or 2,6-CHPh₂-4-Me-C₆H₂ = Ar*) regardless of reaction stoichiometry, with homoleptic bis(ligand) complexes ( ^{^t Bu₂,Dipp}L)₂Mg (1), ( ^{^t Bu₂,Ar*}L)₂Mg (2), ( ^{^t Bu₂,Dipp}L)₂Ca(thf) (3) and ( ^{^t Bu₂,Ar*}L)₂Ca(thf) (4) isolated. The importance of reaction protocol was demonstrated by the facile isolation of heteroleptic complex ( ^{^t Bu₂,Ar*}L)MgI(OEt₂) (5) from the reaction of equimolar amounts of H ^{^t Bu₂,Ar*}L and MeMgI. Importantly, no subsequent ligand redistribution was observed when complex 5 readily reacted with KN" or KODipp to form ( ^{^t Bu₂,Ar*}L)Mg{N(SiMe₃)₂}(OEt₂) (6) and ( ^{^t Bu₂,Ar*}L)Mg(ODipp)(thf) (7). When small 4,6-phenoxide substituents were considered (H^H₂,DippL), multimetallic clusters were afforded: (^H₂,DippL)₃Ca₂(N″)(thf) (8) and (^H₂,DippL)₆Sr₃ (9).

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苯氧亚胺类碱土配合物的核性及结构基序研究。

通过调节配体的立体电子分布、金属的原子序数和合成方案，探讨了双齿苯氧亚胺配体支持的碱土配合物的核性和结构基序。发现改变N-亚胺取代基的大小对[MgN″2]2或CaN″2(thf)2 （N″= N(SiMe3)2）与H- Bu2，ArL （1-OH-2-CH = na -4,6- t Bu-C6H2）之间的质子分解反应没有影响；Ar = 2,6- ipr - c6h3 = Dipp或2,6- chph2 -4- me - c6h2 = Ar*)，不考虑反应的化学计量，与同感的双（配体）配合物（t Bu2,DippL）2Mg (1), (t Bu2,Ar*L)2Mg (2), (t Bu2,DippL)2Ca(thf)(3)和（t Bu2,Ar*L）2Ca(thf)(4)分离。从等摩尔量的H t Bu2，Ar*L和MeMgI反应中容易分离出异感络合物（t Bu2,Ar*L）MgI(OEt2)(5)，证明了反应方案的重要性。重要的是，当配合物5很容易与KN '或KODipp反应形成（t Bu2,Ar*L）Mg{N(SiMe3)2}(OEt2)(6)和（t Bu2,Ar*L）Mg(ODipp)(thf)(7)时，没有观察到随后的配体再分布。当考虑小的4,6-苯取代基（HH2,DippL）时，得到多金属簇：（H2,DippL）3Ca2（N″）（thf）(8)和（H2,DippL）6Sr3(9)。

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.