PC(sp3)P pincer carbonyl complexes of iridium(i), and iridium(iii)

Klara J. Jonasson; Alexey V. Polukeev; Ola F. Wendt

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PC(sp3)P pincer carbonyl complexes of iridium(i), and iridium(iii)

机译：PC（SP3）铱（I）的P in钳子羰基络合物和铱星（III）

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The previously reported complex trans -[IrHCl{ cis -1,3-bis-(di- tert -butylphosphino)methyl}cyclohexane] ( 2 ) forms the 18-electron carbonyl compound anti -[Ir(CO)HCl{ cis -1,3-bis-((di- tert -butylphosphino)methyl)}cyclohexane] ( 5a ) upon reaction with 1 atm CO. The structural isomer syn -[IrH(CO)Cl{ cis -1,3-bis-((di- tert -butylphosphino)methyl)}cyclohexane] ( 5b ) is obtained directly upon complexation of the ligand ( 1 ) with IrCl _(3) ·H _(2) O in refluxing DMF. syn - 5b is the first iridium aliphatic pincer complex with this orientation of the hydrogens and is the thermodynamically more stable isomer. Both compounds 5a and 5b afford the Ir( I ) complex trans -[Ir(CO){ cis -1,3-bis-((di- tert -butylphosphino)methyl)}cyclohexane] ( 4 ) upon treatment with KO ~( t ) Bu. Complex 4 was also synthesised in a more straightforward fashion from the previously known terminal nitrogen complex trans -[Ir(N _(2) ){ cis -1,3-bis-((di- tert -butylphosphino)-methyl)}cyclohexane] ( 3 ) under atmospheric CO. The complexes 4 , 5a and 5b were characterised spectroscopically and in the solid state. IR data point to a more electron rich metal centre as compared to the corresponding aromatic complexes.

机译：先前报道的复杂反式 - [IRHCL {CIS-1,3-双（二叔丁基膦基）甲基}环己烷]（2）形成18-电子羰基化合物抗[IR（CO）HCl {CIS -1 ，3-双 - （（二叔丁基膦基）甲基）}环己烷]（5a）与1atom co反应后。结构异构体SYN - [IRH（CO）CL {CIS -1,3-BIS - （（二叔丁基膦基）甲基）}环己烷]（5B）在回流DMF中用IRCl _（3）·H _（2）O络合在配体（1）络合时直接获得。 SYN-5B是第一种铱脂肽络合物，具有氢的这种取向，是热力学上更稳定的异构体。化合物5A和5B都提供IR（I）复合反式 - [IR（CO）{CIS-1,3-双（（二叔丁基膦基）甲基）}环己烷]（4）在用KO〜（ t）bu。复合物4也以先前已知的末端氮气复合反式 - [IR（N _（2））{CIS-1,3-双 - （（二叔丁基膦基） - 甲基）}环己烷以更直的方式合成。环己烷]（3）在大气中的CO。复合物4,5a和5b的光谱和固态化。与相应的芳族配合物相比，IR数据点进入更富有的金属中心。

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《RSC Advances》 |2015年第20期|共5页
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Klara J. Jonasson; Alexey V. Polukeev; Ola F. Wendt;
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1. PC(sp(3))P pincer carbonyl complexes of iridium(I), and iridium(III) [J] . Jonasson Klara J., Polukeev Alexey V., Wendt Ola F. RSC Advances . 2015,第20期

机译：PC（SP（3））铱（I）的P钳羰基络合物，铱（III）
2. Theoretical Study of POCOP-Pincer Iridium(III)/Iron(II) Hydride Catalyzed Hydrosilylation of Carbonyl Compounds: Hydride Not Involved in the Iridium(III) System but Involved in the Iron(II) System [J] . Wenmin Wang, Piao Gu, Yiou Wang, Organometallics . 2014,第4期

机译：POCOP-辛基铱（III）/铁（II）氢化物催化羰基化合物氢化硅烷化的理论研究：氢化物不参与铱（III）体系，但参与铁（II）体系
3. Theoretical Study of POCOP-Pincer Iridium(III)/Iron(II) Hydride Catalyzed Hydrosilylation of Carbonyl Compounds: Hydride Not Involved in the Iridium(III) System but Involved in the Iron(II) System [J] . Wenmin Wang, Piao Gu, Yiou Wang, Organometallics . 2014,第4期

机译：POCOP-辛基铱（III）/铁（II）氢化物催化羰基化合物氢化硅烷化的理论研究：氢化物不参与铱（III）体系，但参与铁（II）体系
4. Double Cyclometalation: Implications for C-H Oxidative Addition with PCP Pincer Compounds of Iridium [C] . Hani A. Y. Mohammad, Jost C. Grimm, Klaus Eichele, American Chemical Society National Meeting . 2004

机译：双循环级 - 与铱的PCP钳子化合物对C-H氧化添加的影响
5. I. Synthesis and reactivity of chiral iridium(III) and rhodium(III) complexes. II. Platinum-catalyzed iridium-methyl and iridium-phenyl bond formation [D] . Smith, Stuart Edward 2008

机译：I.手性铱（III）和铑（III）配合物的合成和反应性。二。铂催化的铱甲基和铱苯基键的形成
6. Crystal structures of two PCN pincer iridium complexes and one PCP pincer carbodiphosphorane iridium intermediate: substitution of one phosphine moiety of a carbodiphosphorane by an organic azide [O] . Gabriel Julian Partl, Felix Nussbaumer, Walter Schuh, 2019

机译：两种PCN夹钳铱配合物和一种PCP夹钳碳二膦铱铱的晶体结构：有机叠氮化物取代碳二膦烷的一个膦部分
7. PC(sp(3))P pincer carbonyl complexes of iridium(I), and iridium(III) [O] . Jonasson, Klara, Polukeev, Alexey, Wendt, Ola 2015

机译：pC（sp（3））p钳形铱（I）和铱（III）的羰基配合物

PC(sp3)P pincer carbonyl complexes of iridium(i), and iridium(iii)

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