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Synthesis of Pentamethylcyclopentadienyl Dialkynyl Phosphane Iridium(III) complexes. Reactivity of the Complex [Ir(η5-C5Me5)(C≡CPh)2(PPh3)] toward Electrophiles
Organometallics ( IF 2.5 ) Pub Date : 2019-12-19 , DOI: 10.1021/acs.organomet.9b00598
Irene Sánchez-Sordo 1 , Josefina Díez 1 , Elena Lastra 1 , M. Pilar Gamasa 1
Affiliation  

Dialkynyl iridium(III) complexes [Ir(η5-C5Me5)(C≡CPh)2(PPh2R)] (R = Ph (2a), Me (2b), CH2CH═CH2 (2c)) have been prepared by reaction of the complexes [Ir(η5-C5Me5)Cl2(PPh2R)] (R = Ph (1a), Me (1b), CH2CH═CH2 (1c)) and lithium phenylacetylide. Alternatively, complexes 2a,b have been synthesized by the treatment of the complexes [Ir(η5-C5Me5)I2(PPh2R)] (R = Ph (3a), Me (3b)) with [AgC≡CPh]n. The reactivity of the complex [Ir(η5-C5Me5)(C≡CPh)2(PPh3)] (2a) toward electrophiles is reported. Thus, complex 2a reacts with tetrafluoroboric acid to give the new butenynyl complex [Ir(η5-C5Me5){η3-C(Ph)≡CC═C(H)Ph}(PPh3)][BF4] (4) after stirring for 15 min at room temperature. Complex 4 evolves to [Ir(η5-C5Me5){κ4(P,C,C,C)-PPh2C6H4C(Ph)CHC═C(H)Ph}][BF4] (5) after stirring for 24 h at room temperature. The reaction of complex 2a with methyl trifluoromethanesulfonate leads to the formation of the complex [Ir(η5-C5Me5){κ3(C,C,C)-C6H4C(Me)═C═C═C(H)Ph}(PPh3)][CF3SO3] as a 1:1.5 mixture of the Z (6) and E (7) stereoisomers. The structures of complexes 2c, 5, and 7 have been resolved by X-ray diffraction analysis.

中文翻译:

五甲基环戊二烯二炔基膦基铱(III)配合物的合成。的配合物[(ηIr中反应5 -C 55)(C≡CPh)2(PPH 3)]向亲电

Dialkynyl铱(III)配合物的[Ir(η 5 -C 55)(C≡CPh)2(PPH 2 R)](R =苯基(图2a)中,Me(2B),CH 2 CH = CH 22c中))已经被制备的[Ir(η络合物的反应5 -C 55)氯2(PPH 2 R)](R =苯基(1A)中,Me(1B),CH 2 CH = CH 21C))和苯基乙炔化锂。替代地,复合物2ab由复合物的[Ir(η的治疗已被合成5 -C 55)本人2(PPH 2 R)](R =苯基(图3a)中,Me(图3b)),与[AgC≡CPh] Ñ。的配合物[Ir(η的反应性5 -C 55)(C≡CPh)2(PPH 3)](2A报道)朝向电体。因此,复杂2a中与四氟硼酸反应,得到新的butenynyl配合物[Ir(η 5 -C 55){η 3 -C(PH)≡CC═C(H)PH}(PPH3)] [BF 4 ](4)在室温下搅拌15分钟后。复杂4个演变与[Ir(η 5 -C 55){κ 4PçÇÇ)-PPh 2 ç 6 ħ 4 C(PH)CHC═C(H)PH}] [BF 4在室温下搅拌24小时后的(5)。复合物的反应图2a用三氟甲磺酸甲酯通向配合物[Ir(η形成5 -C 55){κ3CCC)-C 6 H 4 C(Me)═C═C═C(H)Ph}(PPh 3)] [CF 3 SO 3 ]作为Z6的1:1.5混合物))和E7)立体异构体。配合物2c57的结构已经通过X射线衍射分析解析。
更新日期:2019-12-19
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