Anion-induced migration reaction of acetylide from iron to cyclopentadienyl in (cyclopentadienyl)irondicarbonyl(acetylide) complexes

Liu, Ling‐Kang; Chang, Kuo-Yang; Wen, Yuh‐Sheng

doi:10.1039/a709100a

Cited by 14 publications

(3 citation statements)

References 24 publications

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“…The first example of this type of migration reaction was reported by Dean and Graham in 1977 for M(η 5 -C 5 H 5 )(GePh 3 )(CO) 3 (M = Mo, W) . Since then, several types of migrations have been observed: silyl from rhenium and iron, germyl, stannyl, and plumbyl from molybdenum, tungsten, and iron, 3e, acyl from rhenium 5 and iron, hydride from rhenium 7 and iron, acetylide from iron, and phosphorus ligands from iron 10 and ruthenium …”

Section: Introductionmentioning

confidence: 97%

Generation of Functionally Substituted Cyclopentadienyl Ligands in Osmium(IV) Chemistry

et al. 2000

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Several types of substituted cyclopentadienyl osmium(IV) complexes can be obtained by reaction of OsH(η5-C5H5)Cl(EPh3)(PiPr3) (E = Ge (1), Si (2)) with LiNu reagents. Both 1 and 2 react with LiCH2CN. The reactions give OsH2(η5-C5H4EPh3)(CH2CN)(PiPr3) (E = Ge (3), Si (4)). The reaction of the perdeuterated cyclopentadienyl complex OsH(η5-C5D5)Cl(SiPh3)(PiPr3) (2-d 5 ) with LiCH2CN affords Os(H)(D)(η5-C5D4SiPh3)(CH2CN)(PiPr3) (4-d 5 ). Complex 4 reacts with CD3OD to give OsH2(η5-C5H4SiPh3)(CD2CN)(PiPr3) (4-d 2 ), which can be also obtained by addition of LiCD2CN to 2. The treatment of 1 with RLi leads to OsH2(η5-C5H4R)(GePh3)(PiPr3) (R = CH3 (5), nBu (6), secBu (7)). Under the same conditions, the addition of nBuLi to OsH(η5-C5D5)Cl(GePh3)(PiPr3) (1-d 5 ) affords Os(H)(D)(η5-C5D4 nBu)(GePh3)(PiPr3) (6-d 5 ). Complex 2 also reacts with CH3Li and nBuLi. In both cases, complex (8) is obtained. The structure of 8 has been determined by X-ray diffraction analysis. The distribution of ligands around the metallic center can be described as a four-legged piano stool geometry with the phosphine and the metalated phenyl group mutually transoid. The treatment at room temperature of 2-d 5 with nBuLi leads to a mixture of (8-d 4 ) and Os(H)(D)(η5-C5D4 n Bu)(SiPh3)(PiPr3) (9-d 5 ) in a 2:1 molar ratio. The reaction of 2 with secBuLi also gives a mixture. In this case, it is formed by OsH2(η5-C5H4 secBu)(SiPh3)(PiPr3) (10) and 8 in a 1:4 molar ratio. The addition of LiCH2C(O)CH3 to 2 leads to (11). The reactions of 1 with LiNR2 afford OsH2(η5-C5H4NR2)(GePh3)(PiPr3) (R = Et (12), allyl (13)), while under the same conditions 2 gives mixtures of 8 and OsH2(η5-C5H4NR2)(SiPh3)(PiPr3) (R = Et (14), allyl (15)). The structure of 13 has been also determined by X-ray diffraction analysis. The distribution of ligands around the metallic center is also a four-legged piano stool geometry, but in this case, the phosphine is transoid to GePh3. Both 1 and 2 react with LiPPh2. The reactions give the cyclopentadienyl phosphine derivatives OsH2(η5-C5H4PPh2)(EPh3)(PiPr3) (E = Ge (16), Si (17)).

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Section: Introductionmentioning

confidence: 97%

Generation of Functionally Substituted Cyclopentadienyl Ligands in Osmium(IV) Chemistry

et al. 2000

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“…This unique reaction is induced by a strong base. The migrating ligands include acyl, alkoxycarbonyl,1d formyl, 1e,g acetylide, silyl, germyl, 3k, stannyl,4b plumbyl,4b hydride, and phosphorus ligands . In addition, polysilane migration to the Cp ring with alkyl rearrangement 3f has been reported.…”

Section: Introductionmentioning

confidence: 99%

Novel Phosphine- and Phosphite-Induced Imido Migration to a Cyclopentadienyl Ring in an Imido-Bridged Cobaltadithiolene Complex

et al. 2002

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“…Deprotonation of this unstable carbenium product, which does not undergo acetylide migration, in the presence of some weak nucleophiles readily gives back 7d . Reversed migration of an acetylide group from an Fe metal to a cyclopentadienyl ligand has been reported recently . In our system the migration is from the exocyclic C α of a substituted group on the Cp ligand to the metal.…”

Section: Resultsmentioning

confidence: 99%

New Acetylide Migration and Oxygen Transfer Reactions in Ruthenium Complexes Containing an Acetyl-Substituted Cp Ligand

et al. 2002

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Formation of [η 5 :η 1 -C 5 H 4 C(CH 3 )dC(Ph)C(O)](PPh 3 ) 2 Ru (3a) from the reaction of (η 5 -C 5 H 4 -COCH 3 )(PPh 3 ) 2 RuCl (2a) with PhCtCH proceeds via the vinylidene intermediate [(η 5 -C 5 H 4 -COCH 3 )(PPh 3 ) 2 RudCdCHPh]Cl (4a). In this reaction the oxygen atom of the pendant acetyl group in the cyclopentadienyl ligand of 4a is transferred to C R of the vinylidene ligand, and this transfer is accompanied by formation of a CdC bond, giving 3a. Treatment of 2a with LiCtCPh affords (η 5 -C 5 H 4 C(CCPh)(OH)CH 3 )(PPh 3 ) 2 RuCl (6a), and passing 6a through a column packed with alumina also gives 3a. The latter transformation involves a new migration of an acetylide group from exocyclic C R of a substituted cyclopentadienyl ligand to the Ru center followed by the same oxygen transfer process. The metal acetylide (η 5 -C 5 H 4 COCH 3 )(BINAP)RuCtCPh (5c), resulting from the same migration but with no oxygen transfer, is isolated when two PPh 3 ligands are replaced by BINAP. The structures of complexes 3a and 6b, a chirophos analogue of 6a, have been determined by X-ray diffraction analysis.

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Anion-induced migration reaction of acetylide from iron to cyclopentadienyl in (cyclopentadienyl)irondicarbonyl(acetylide) complexes

Cited by 14 publications

References 24 publications

Generation of Functionally Substituted Cyclopentadienyl Ligands in Osmium(IV) Chemistry

Generation of Functionally Substituted Cyclopentadienyl Ligands in Osmium(IV) Chemistry

Novel Phosphine- and Phosphite-Induced Imido Migration to a Cyclopentadienyl Ring in an Imido-Bridged Cobaltadithiolene Complex

New Acetylide Migration and Oxygen Transfer Reactions in Ruthenium Complexes Containing an Acetyl-Substituted Cp Ligand

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