2000
DOI: 10.1021/om990874y
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Synthesis and Migratory Insertion Reactions of (Vinylidene)iridium Complexes trans-[IrX(CCRR‘)(PiPr3)2] Containing Alkyl, Aryl, Alkynyl, and Azide Ligands,1

Abstract: The (vinylidene)iridium(I) complexes trans-[IrCl(dCdCRR′)(PiPr 3 ) 2 ] (1, 4) react with organolithium compounds R′′Li by chloride substitution to afford the organoiridium(I) derivatives trans-[IrR′′(dCdCRR′)(PiPr 3 ) 2 ] (5-8) in excellent yields. In contrast, treatment of 1 (R ) SiMe 3 , R′ ) Me) with Grignard reagents R′′MgX leads to halide metathesis and formation of the bromo-and iodoiridium(I) compounds trans-[IrX{dCdC(SiMe 3 )Me}(PiPr 3 ) 2 ] (X ) Br, I), respectively. The alkynyl complexes trans-[Ir(Ct… Show more

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Cited by 27 publications
(13 citation statements)
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“…[17] Passing a slow stream of CO through a solution of 17 (generated in situ) in pentane causes a change of color from orange to yellow and gives the carbonyl complex 18 as a yellow solid in 85 % yield. However, the assumption that the migratory insertion of the C 4 unit into the Ir À CH 3 bond has led to a product of composition trans-[Ir{C(CH 3 )CC CPh 2 }(CO)(PiPr 3 ) 2 ] is not in agreement with the 1 H NMR spectrum which instead of a triplet at around d 1.85 ± 1.95 for the IrC(CH 3 ) protons [18] displays a singlet at d 1.62. Moreover, the 13 C NMR spectrum of 18 differs from that of 16 with an IrCHCCCPh 2 fragment insofar as only two resonances for the 13 C nuclei of the IrC 4 chain exhibit a 13 C ± 31 P coupling of, respectively, 12.7 and 4.3 Hz.…”
Section: Addition Reactions Of Complex 8 With Co and Br˘nsted Acidsmentioning
confidence: 93%
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“…[17] Passing a slow stream of CO through a solution of 17 (generated in situ) in pentane causes a change of color from orange to yellow and gives the carbonyl complex 18 as a yellow solid in 85 % yield. However, the assumption that the migratory insertion of the C 4 unit into the Ir À CH 3 bond has led to a product of composition trans-[Ir{C(CH 3 )CC CPh 2 }(CO)(PiPr 3 ) 2 ] is not in agreement with the 1 H NMR spectrum which instead of a triplet at around d 1.85 ± 1.95 for the IrC(CH 3 ) protons [18] displays a singlet at d 1.62. Moreover, the 13 C NMR spectrum of 18 differs from that of 16 with an IrCHCCCPh 2 fragment insofar as only two resonances for the 13 C nuclei of the IrC 4 chain exhibit a 13 C ± 31 P coupling of, respectively, 12.7 and 4.3 Hz.…”
Section: Addition Reactions Of Complex 8 With Co and Br˘nsted Acidsmentioning
confidence: 93%
“…As shown in Figure 2, the coordination geometry around the metal center corresponds to a square plane, the distortion of which is less pronounced than in the related vinyl complex trans-[Ir{C(CH 3 )C(SiMe 3 )Me}(CO)(PiPr 3 ) 2 ]. [18] The two phosphine ligands are trans to each other with an eclipsed conformation along the P-Ir-P axis. This axis is not exactly linear, however, the bond angle of 167.64(4)8 being about 4.58 nearer to the 1808 value than in the above-mentioned IrC(CH 3 )C(SiMe 3 )Me derivative.…”
Section: Addition Reactions Of Complex 8 With Co and Br˘nsted Acidsmentioning
confidence: 99%
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“…We found that the chloride cannot only be replaced by other halides but equally by pseudohalides such as OCN À , SCN À , or N 3 À and even by hydroxide and similar O-donor ligands. However, in contrast to the vinylidene analogues trans-[IrCl{CC(Ph)R}(PiPr 3 ) 2 ], which react with organolithium compounds R'Li to give the substitution products trans-[Ir(R'){CC(Ph)R}(PiPr 3 ) 2 ] in excellent yields, [3] our attempts to obtain the related allenylidene derivatives trans-[Ir(R'){CCC(Ph)R}(PiPr 3 ) 2 ] failed. For this reason we were unable to carry out C À C coupling reactions, for example with CO, which in the case of the vinylidene complexes trans-[Ir(R'){CC(Ph)R}(PiPr 3 ) 2 ] led by migratory insertion of the CC(Ph)R fragment into the IrÀR' bond to substituted vinyl units.…”
Section: Introductionmentioning
confidence: 89%
“…For this reason we were unable to carry out C À C coupling reactions, for example with CO, which in the case of the vinylidene complexes trans-[Ir(R'){CC(Ph)R}(PiPr 3 ) 2 ] led by migratory insertion of the CC(Ph)R fragment into the IrÀR' bond to substituted vinyl units. [3] Therefore, we turned our interest to the reactivity of the compounds trans-[IrCl{CCC(Ph)R}(PiPr 3 ) 2 ] towards HCl, CH 3 I, and other electrophiles with the particular aim to find out whether the electrophilic substrates would preferentially attack the electron-rich metal center or the highly unsaturated IrC 3 moiety. Herein we report that both reaction paths are possible and that, depending on the nature of the attacking reagent, the allenylidene unit can be converted into butatriene, carbene, and carbyne ligands.…”
Section: Introductionmentioning
confidence: 99%