Der erste strukturell charakterisierte Metallkomplex mit dem Molekülbaustein MCCCCR2

Ilg, Kerstin; Werner, Helmut

doi:10.1002/(sici)1521-3757(20000502)112:9<1691::aid-ange1691>3.0.co;2-x

Cited by 12 publications

(4 citation statements)

References 25 publications

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“…We assume that steric effects also explain why the dihedral angle between the planes [Ir,Cl,P1,P2] and [C1,C2,C8] is not 0° (as suggested by bonding arguments) but is 67.3(3)° and thus deviates significantly from the expected value. The Ir−C1 bond length (1.887(5) Å) is longer than in the vinylidene and butatrienylidene iridium analogues, trans -[IrCl(CCHCO 2 Me)(P i Pr 3 ) 2 ] (1.764(6) Å) 16b and trans -[IrCl(CCCCPh 2 )(P i Pr 3 ) 2 ] (1.816(6) Å), and is almost the same as in the methylene complex [Ir(CH 2 ){κ 3 -N(SiMe 2 CH 2 PPh 2 ) 2 }] (1.868(9) Å) 2 Molecular diagram of compound 14 .…”

Section: Resultsmentioning

confidence: 95%

“…, 19, 1231Chem. -1236 PiPr 3 ) 2 ] (1.764(6) Å) 16b and trans-[IrCl(dCdCdCdCPh 2 )(PiPr 3 ) 2 ] (1.816( 6) Å), 19 and is almost the same as in the methylene complex [Ir(dCH 2 ){κ 3 -N(SiMe 2 CH 2 PPh 2 ) 2 }] (1.868( 9) Å). 20 The reactivity of the structurally related molecules 8 and 14 toward NaC 5 H 5 is quite different.…”

Section: Introductionmentioning

confidence: 91%

“…31 P NMR (81.0 MHz, CD2Cl2): δ 38.2 (s). 19 F NMR (188.3 MHz, CD2Cl2): δ -153.6 (s). MS (FAB; o-nitrophenyloctyl ether as matrix): m/z 715 (M + ).…”

Section: Preparation Of Trans-[ircl{dc(p-c6h4cl)2}(pipr3)2] (16)mentioning

confidence: 99%

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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: 95%

Section: Introductionmentioning

confidence: 91%

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

et al. 2002

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“…This is in contrast to Ir‐C 4 and Mn‐C 4 cumulenic species 3a. 9 Prolonged storage of 3 in solution at room temperature resulted in [3,3′‐bis{ trans ‐(4‐ p ‐ tert ‐butylphenylbuta‐3‐en‐1‐yl)bis(tetraphenyl‐1,2‐diphosphinoethane)carbonyltungsten}] ( 4 ; Scheme ), and diffusion of pentane into a benzene solution of 3 gave brown crystals of the coupled molecule in 53 % yield. Formation of 4 can be envisaged to occur by coupling at the C3 atom of 3 with subsequent rearrangement of the diphosphine ligands from cis to trans 7.…”

Section: Methodsmentioning

confidence: 99%

A Rare Example of a Rearrangement Involving Four Structural Isomers: -Phosphinonitrile/C-Phosphinoketenimine/1-Aza-4-phosphabutadiene/ 1,2-Dihydro-1,2-azaphosphete

et al. 2002

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The stable compound [bis(dicyclohexylamino)phosphino](trimethylsilyl)carbene (1) reacts with dimethyl cyanamide to afford the original 1,2-dihydro-1,2azaphosphete 4 a (51 % yield). The surprising formation of this heterocycle involves the transient formation of a nitrile, a keteneimine, and a 1-aza-4l 3 -phosphabutadiene derivative. By using substituent effects and different synthetic routes, all of these structural isomers have been isolated.

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Cationic Five-Coordinate Bis(butadiene)iridium(I) Complexes from the Highly Labilecis-[Ir(η2-C8H14)2(acetone)2]+ Cation as the Precursor

Bosch

Ilg

Werner

2001

Eur. J. Inorg. Chem.

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The cation cis‐[Ir(η2‐C8H14)2(acetone)2]+, which is generated in situ from [Ir(μ‐Cl)(η2‐C8H14)2]2 (1) and AgPF6 in acetone, reacts with butadiene at room temperature to give the five‐coordinate complex [Ir(s‐cis‐η4‐C4H6)2(η2‐C8H14)]PF6 (3). The cyclooctene ligand of 3 is only weakly coordinated and easily displaced by PiPr3, AsiPr3 and SbiPr3 to afford the compounds [Ir(s‐cis‐η4‐C4H6)2(EiPr3)]PF6 (5−7) in excellent yields. Alternatively, 5−7 can be prepared from [IrCl(s‐cis‐η4‐C4H6)2] (4) by stepwise treatment with AgPF6 and EiPr3 (E = P, As, Sb). The X‐ray crystal structure analysis of 5 revealed a square‐pyramidal geometry of the cation with the phosphane ligand in the apical position.

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Der erste strukturell charakterisierte Metallkomplex mit dem Molekülbaustein MCCCCR2

Cited by 12 publications

References 25 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

A Rare Example of a Rearrangement Involving Four Structural Isomers: -Phosphinonitrile/C-Phosphinoketenimine/1-Aza-4-phosphabutadiene/ 1,2-Dihydro-1,2-azaphosphete

Cationic Five-Coordinate Bis(butadiene)iridium(I) Complexes from the Highly Labilecis-[Ir(η2-C8H14)2(acetone)2]+ Cation as the Precursor

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