Palladium(II), Platinum(II), and Iridium(I) Complexes of 2-Phosphino-1-dimethylaminoferrocenes: A Survey of Structure and Catalysis

Metallinos Costa; Zaifman Josh; Van Belle Lori; Dodge Laura; Pilkington Melanie

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Palladium(II), Platinum(II), and Iridium(I) Complexes of 2-Phosphino-1-dimethylaminoferrocenes: A Survey of Structure and Catalysis

机译：2-磷酸-1-二甲基氨基二茂铁的钯（II），铂（II）和铱（I）配合物：结构和催化作用的研究

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A series of PdCl2, PtCl2 and Ir(COD)BArF. complexes bearing a rare class of racemic bidentate 2-phosphino-1-dimethylaminoferrocene ligands were prepared and characterized by NMR spectroscopy and X-ray crystallography. The new complexes displayed a structural trend relating a decrease in heteroatom-metal bond length with an increase in ligand bite angle on going from Ir to Pd and Pt. The pdCl(2) and PtCl2 complexes were almost isostructural and featured MCl2 moieties in the plane of the substituted Cp ring of the ligand. In contrast, the Ir(COD)(4)complex was distinguished by a bend of the Ir(COD) moiety toward the unsubstituted (Cp') ring. The latter gave rise to a steric interaction that placed the Cp rings in almost eclipsed conformations. Ligand 8a (2-diphenylphosphino-1-dimethylaminoferrocene) was able to promote Pd-catalyzed Suzuki-Miyaura and Buchwald-Hartwig coupling of aryl chlorides in addition to Ir-catalyzed hydrogeriation of electron-deficient and unactivated alkenes. A preliminary intramolecular hydroamination of a terminal alkene using 8a in conjunction with lr(l) afforded the cyclized product in 64% yield.

机译：一系列PdCl2，PtCl2和Ir（COD）BArF。制备了带有稀有外消旋二齿2-膦基-1-二甲基氨基二茂铁配体的配合物，并通过NMR光谱和X射线晶体学表征。新的配合物显示出一种结构趋势，即从Ir到Pd和Pt时，杂原子-金属键长度的减少与配体咬合角的增加有关。 pdCl（2）和PtCl2络合物几乎是同构结构，并在配体的取代Cp环平面内具有MCl2部分。相反，Ir（COD）（4）络合物的特征是Ir（COD）部分朝向未取代的（Cp'）环弯曲。后者引起空间相互作用，使Cp环处于几乎黯淡的构象。配体8a（2-二苯基膦基-1-二甲基氨基二茂铁）能够促进钯催化的芳基氯化物的Suzuki-Miyaura和Buchwald-Hartwig偶联，以及Ir催化的缺电子和未活化烯烃的加氢萌芽。使用8a与lr（l）进行的末端烯烃的初步分子内加氢胺化反应以64％的收率获得了环化产物。

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来源
《Organometallics》 |2009年第15期|共10页
作者
Metallinos Costa; Zaifman Josh; Van Belle Lori; Dodge Laura; Pilkington Melanie;
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正文语种 eng
中图分类 545B0014-1;
关键词
DENSITY-FUNCTIONAL THEORY; ASYMMETRIC HYDROGENATION; ENANTIOSELECTIVE HYDROGENATION; OXIDATIVE ADDITION; BOND FORMATION; LIGANDS; AMINATION; OLEFINS; ALKENES; KETONES;

机译：密度泛函理论;不对称加氢;对映选择性加氢;氧化加成;键形成;配体;胺化;烯烃;烯烃;酮;

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1. Palladium(II), Platinum(II), and Iridium(I) Complexes of 2-Phosphino-1-dimethylaminoferrocenes: A Survey of Structure and Catalysis [J] . Metallinos Costa, Zaifman Josh, Van Belle Lori, Organometallics . 2009,第15期

机译：2-磷酸-1-二甲基氨基二茂铁的钯（II），铂（II）和铱（I）配合物：结构和催化作用的研究
2. Synthesis and characterization of palladium(II) and platinum(II) metal complexes with iminophosphine ligands: X-ray crystal structures of platinum(II) complexes and use of palladium(II) complexes as pre-catalysts in Heck and Suzuki cross-coupling reactions [J] . Haleden Chiririwa, Freeman Ntuli, Edison Muzenda Transition Metal Chemistry . 2013,第4期

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3. Metal complexes of biologically important ligands. CIII. Palladium(Il), platinum(II), ruthenium(II), rhodinum(III), and iridium(III) complexes of desoxyfructosazine [German] [J] . Krawielitzki S., Beck W. Zeitschrift fur Anorganische und Allgemeine Chemie . 1998,第10期

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4. Theoretical Studies on the Electronic Structures and Spectral Properties of Two Iridium(III) Complexes with Tetraphenylimidodiphosphinate Ligand [C] . Han De-ming, Zhang Gang, Zhao Li-hui International Conference onuture Optical Materials and Circuit Design . 2013

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Palladium(II), Platinum(II), and Iridium(I) Complexes of 2-Phosphino-1-dimethylaminoferrocenes: A Survey of Structure and Catalysis

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