Iridium(I)- und Iridium(III)-Komplexe mit Triisopropylarsan als Ligand

Werner, Helmut; Ortmann, Dagmara A.; Ilg, Kerstin

doi:10.1002/1521-3749(200012)626:12<2457::aid-zaac2457>3.0.co;2-k

Cited by 4 publications

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“…Typical spectroscopic features of 6 are the two high-field 1 H NMR resonances for the cis -disposed hydrides at δ −10.89 and −28.24 and the two sets of signals for the protons and carbon atoms of the diastereotopic CH 3 groups of the Sb i Pr 3 and P i Pr 3 ligands in the 1 H and 13 C NMR spectra. The IR spectrum of 6 displays two bands for the Ir−H stretching modes at 2201 and 2093 cm -1 , the positions being nearly identical to those of the related bis(arsine) complex cis,trans -[IrH 2 Cl(C 2 H 4 )(As i Pr 3 ) 2 ] 2 …”

Section: Resultsmentioning

confidence: 86%

Carbene Iridium(I) and Iridium(III) Complexes Containing the Metal Center in Different Stereochemical Environments

et al. 2002

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The mixed-ligand complex [IrCl(C2H4)(SbiPr3)(PiPr3)] (2), prepared from [IrCl(C2H4)(PiPr3)]2 (1) and SbiPr3, reacts not only with CO, diphenylacetylene, and H2 by ligand substitution or oxidative addition but also with diaryldiazomethanes R2CN2 to give the four-coordinate iridium(I) carbenes [IrCl(CR2)(SbiPr3)(PiPr3)] (8−10) in 60−70% isolated yield. In contrast, treatment of 2 and of the related cyclooctene derivative trans-[IrCl(C8H14)(SbiPr3)2] (12) with C5Cl4N2 affords the diazoalkane complexes trans-[IrCl(N2C5Cl4)(SbiPr3)(EiPr3)] (11, E = P; 13, E = Sb) without elimination of N2. Displacement of the stibine ligand in 8−10 by PiPr3 leads to the corresponding bis(phosphine) compounds trans-[IrCl(CR2)(PiPr3)2] (14−16), while the reaction of 8 (R = C6H5) with NaC5H5 yields the half-sandwich-type complex [(η5-C5H5)Ir(CPh2)(PiPr3)] (17). Protonation of 17 with HCl occurs stepwise to give via the iridium(III) alkyl [(η5-C5H5)IrCl(CHPh2)(PiPr3)] (20) the ring-substituted isomer [(η5-C5H4CHPh2)IrHCl(PiPr3)] (21); however, if 17 is treated with HBF4, a cationic complex is formed which probably contains a η3-coordinated benzylic ligand. The square-planar iridium(I) carbenes 8 and 14 react with HBX4 (X = F, ArF) to afford the ionic products [IrHCl(CPh2)(PiPr3)(EiPr3)]BX4 (23, 24, E = P; 25, E = Sb) and with HCl to give the relatively labile octahedral species [IrHCl2(CPh2)(PiPr3)(EiPr3)] (26, E = P; 27, E = Sb). Treatment of 8 and 14 with ethene yields, besides [IrCl(C2H4)2(SbiPr3)2] (18) and/or trans-[IrCl(C2H4)(PiPr3)2] (28), a mixture of two isomeric olefinic products CH2CHCHPh2 (29) and CH3CHCPh2 (30), the ratio of which is independent of the ligand sphere of the iridium precursor. The molecular structures of 13, 14, 17, and 24 have been determined by X-ray crystallography.

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Section: Resultsmentioning

confidence: 86%

Carbene Iridium(I) and Iridium(III) Complexes Containing the Metal Center in Different Stereochemical Environments

et al. 2002

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“…The Ir−C1 bond lies not exactly perpendicular to the basal plane of the pyramide but is slightly bent toward the carbon atom C50. The distance Ir−C1 (1.998(6) Å) is marginally shorter than the Ir−C40 and Ir−C50 bond lengths (2.020(6) and 2.018(6) Å) but virtually identical to the Ir−C distance in the six-coordinate (vinyl)iridium(III) complex [IrHCl(CHCH 2 )(NCMe)(P i Pr 3 ) 2 ] (1.99(2) Å) . The carbon−carbon bond lengths C1−C2, C3−C4, and C4−C5 (1.35(1), 1.32(1), and 1.31(1) Å) are significantly shorter than the distance C2−C3 (1.46(1) Å), which confirms the presence of an allenylvinyl ligand.…”

Section: Resultsmentioning

confidence: 93%

Substitution and Migratory Insertion Reactions of Square-Planar Allenylidene Iridium Complexes

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Werner

2001

Organometallics

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A series of (allenylidene)iridium(I) complexes of general composition trans-[IrX{dCdCd C(Ph)R}(PiPr 3 ) 2 ] [X ) Br ( 5), I (6), NCO (7, 8), NCS (9, 10), OH (11, 12), N 3 (13, 14)] was prepared from the corresponding chloro derivatives trans-[IrCl{dCdCdC(Ph)R}(PiPr 3 ) 2 ] (3, 4) by salt metathesis. An X-ray crystal structure analysis of 4 (R ) Ph) confirmed the almost linear arrangement of the Ir-C-C-C chain. The azido compounds 13 (R ) Ph) and 14 (R ) tBu) react with CO by migratory insertion of the allenylidene ligand into the Ir-N 3 bond. While the product trans-[Ir{C≡C-CR(Ph)N 3 }(CO)(PiPr 3 ) 2 ] with R ) tBu ( 16) is thermally stable, the related complex with R ) Ph ( 15) rearranges slowly in benzene to the metalated acrylonitrile derivative trans-[Ir{C(CN)dCPh 2 }(CO)(PiPr 3 ) 2 ] (17) by elimination of N 2 . Treatment of the phenolato compound trans-[Ir(OPh){dCdCdC(Ph)tBu}(PiPr 3 ) 2 ] (19), obtained from the analogous hydroxo derivative 12 and phenol, with CO also proceeds by migratory insertion and affords the functionalized (alkynyl)iridium(I) complex trans-[Ir{Ct C-CtBu(Ph)OPh}(CO)(PiPr 3 ) 2 ] (20) in excellent yield. The Lewis basicity of the hydroxo compounds 11 and 12 was also illustrated by the reactions with CF 3 CO 2 H, NEt 3 ‚3HF, and [pyH]BF 4 , which gave the substitution products trans-[Ir(κ 1 -O 2 CCF 3 ){dCdCdC(Ph)tBu}-(PiPr 3 ) 2 ] (21), trans-[IrF(dCdCdCPh 2 )(PiPr 3 ) 2 ] (22), and trans-[Ir{dCdCdC(Ph)tBu}(py)-(PiPr 3 ) 2 ]BF 4 (23), respectively. In methanol solution, both 11 and 12 react by complete fragmentation of 1 equiv of CH 3 OH to afford the octahedral (allenyl)dihydridoiridium(III) complexes [IrH 2 {CHdCdC(Ph)R}(CO)(PiPr 3 ) 2 ] (24, 25). An unprecedented type of insertion reaction occurs by treating the hydroxo derivatives 11 and 12 with an excess of 1-alkynes R′CtCH (R′ ) Ph, CO 2 Me), which leads to the formation of the novel five-coordinate iridium-(III) compounds [Ir(CtCR′) 2 {η 1 -(E)-CHdCR′-CHdCdC(Ph)R}(PiPr 3 ) 2 ] (26-29). From 26, 27 (R′ ) Ph), and CO, the octahedral 1:1 adducts 30 and 31 are formed. The molecular structures of 22 and 26 have been determined by X-ray crystallography.

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Iridium

Yellowlees

Macnamara

2003

Comprehensive Coordination Chemistry II

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Iridium(I)- und Iridium(III)-Komplexe mit Triisopropylarsan als Ligand

Cited by 4 publications

References 10 publications

Carbene Iridium(I) and Iridium(III) Complexes Containing the Metal Center in Different Stereochemical Environments

Carbene Iridium(I) and Iridium(III) Complexes Containing the Metal Center in Different Stereochemical Environments

Substitution and Migratory Insertion Reactions of Square-Planar Allenylidene Iridium Complexes

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