Change in Coordination of NCN Pincer Iron Complexes Containing Bis(oxazolinyl)phenyl Ligands
Change in Coordination of NCN Pincer Iron Complexes Containing Bis(oxazolinyl)phenyl Ligands
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DOI：
10.1021/om300901k
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发表时间：
2012-11
期刊：
影响因子：
2.8
通讯作者：
Satomi Hosokawa;Jun-Ichi Ito;H. Nishiyama
中科院分区：
文献类型：
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作者：
Satomi Hosokawa;Jun-Ichi Ito;H. Nishiyama
研究了（phebox-R）Fe(CO)2Br （1a: R = Me2; 1b: R = i-Pr）与膦和异氰化物的配位反应。1与过量的PMe3在甲苯中在50℃下反应得到相应的阳离子配合物[(phebox-R)Fe(CO)(PMe3)2]Br [2a: R = Me2 (79%)]；[2] R = i-Pr（83%）。通过x射线衍射分析证实了2a和2b的分子结构，发现其为伪八面体，具有NCN子午配位。1与PMe2Ph反应得到中性膦络合物（η - 2-phebox-R）Fe(CO)(PMe2Ph)2Br [3a: R = Me2 (87%)；3b: R = i-Pr(79%)]，其中phebox配体与Fe作为NC双齿配体配以恶唑啉和苯基。中性膦配合物3a的后续反应通过改变配位形成相应的阳离子配合物[(phebox-Me2)Fe(CO)(PMe2Ph)2]Br(4)。
The coordination of bis(oxazolinyl)phenyl (phebox) ligands to an Fe center was investigated in the reaction of (phebox-R)Fe(CO)2Br (1a: R = Me2; 1b: R = i-Pr) with phosphine and isocyanide compounds. Reaction of 1 with an excess amount of PMe3 in toluene proceeded at 50 °C to give the corresponding cationic complexes [(phebox-R)Fe(CO)(PMe3)2]Br [2a: R = Me2 (79%); 2b: R = i-Pr (83%)]. The molecular structures of 2a and 2b were confirmed by X-ray diffraction analysis that revealed the pseudo-octahedral geometry with NCN meridional coordination of the phebox ligand. In contrast, reaction of 1 with PMe2Ph gave the neutral phosphine complexes (η2-phebox-R)Fe(CO)(PMe2Ph)2Br [3a: R = Me2 (87%); 3b: R = i-Pr (79%)], in which the phebox ligand was coordinated to Fe as an NC bidentate ligand with the oxazoline and phenyl groups. Subsequent reaction of the neutral phosphine complex 3a resulted in the formation of the corresponding cationic complexes [(phebox-Me2)Fe(CO)(PMe2Ph)2]Br (4) via change in coordination to ...