Phosphorane Migration from Ruthenium to the Cyclopentadienyl Ring

Nakazawa, Hiroshi; Kawamura, Kohei; Kubo, Kazuya; Miyoshi, Katsuhiko

doi:10.1021/om9904145

Cited by 15 publications

(5 citation statements)

References 18 publications

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“…In many cases the hydride complex bears a cyclopentadienyl ligand, which is known to have rather acidic C−H bonds. In agreement with the acidity of the η 5 -C 5 H 5 group, cyclopentadienyl complexes of molybdenum, tungsten, rhenium, iron, and ruthenium undergo base-induced migration reactions of a monodentate ligand from the metal to a neighboring cyclopentadienyl carbon atom. It is widely accepted that such reactions involve the initial deprotonation of the cyclopentadienyl ring followed by the ligand migration.…”

Section: Introductionmentioning

confidence: 61%

Influence of the Group 14 Element on the Deprotonation of OsH(η⁵-C₅H₅)(C⋮CPh)(EPh₃)(PⁱPr₃) (E = Si, Ge): Two Different Organometallic Chemistries

2001

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The complexes OsH(η 5-C5H5)Cl(EPh3)(PiPr3) (E = Si (1), Ge (2)) react with lithium phenylacetylide to give the hydride−alkynyl derivatives OsH(η 5-C5H5)(C⋮CPh)(EPh3)(PiPr3) (E = Si (3), Ge (4)). The structure of 4 has been determined by X-ray diffraction analysis. The distribution of ligands around the osmium atom can be described as a four-legged piano-stool geometry with the monodentate ligands lying in the four-membered face. Treatment of 3 with n-butyllithium and the subsequent addition of methanol, methanol-d 4, and methyl iodide to the resulting solution leads to OsH(η 5-C5H4SiPh3){CC(H)Ph}(PiPr3) (5), OsH(η 5-C5H4SiPh3){CC(D)Ph}(PiPr3) (5- d ), and (6), respectively. Similarly to 3, the reaction of the perdeuterated cyclopentadienyl complex OsH(η 5-C5D5)(C⋮CPh)(SiPh3)(PiPr3) (3- d 5 ) with n-butyllithium and methanol gives OsH(η 5-C5D4SiPh3){CC(H)Ph}(PiPr3) (5- d 4 ). The structure of 6 has been also determined by X-ray diffraction analysis. In this case, the distribution of ligands around the osmium atom can be described as a piano-stool geometry with the metalated carbon atom transoid to the phosphine and cisoid to the hydride. Complex 5 reacts with HBF4 to give the hydride−carbyne derivative [OsH(η 5-C5H4SiPh3)(⋮CCH2Ph)(PiPr3)]BF4 (7), which is stable. Initially, the addition of HBF4 to diethyl ether solutions of 6 also leads to a hydride−carbyne complex, [OsH(η 5-C5H4SiPh3){⋮CCH(CH3)Ph}(PiPr3)]BF4 (8). However, in solution, complex 8 evolves into the hydride−allyl compound [OsH(η 5-C5H4SiPh3){η 3-CH2C(Ph)CH2}(PiPr3)]BF4 (9). The structure of 9 has been determined by X-ray diffraction analysis. The distribution of ligands around the osmium atom can be described as a piano-stool geometry, where the allyl ligand occupies two cisoid positions. Treatment of 4 with n-butyllithium and the subsequent addition of methanol, methanol-d 4, and methyl iodide to the resulting solution gives the germyl−vinylidene complexes Os(η 5-C5H5)(GePh3){CC(H)Ph}(PiPr3) (10), Os(η 5-C5H4D)(GePh3){CC(D)Ph}(PiPr3) (10- d 2 ), and Os(η 5-C5H4CH3)(GePh3){CC(CH3)Ph}(PiPr3) (11), respectively. The protonation of 10 and 11 with HBF4 affords the corresponding carbyne derivatives [Os(η 5-C5H5)(GePh3)(⋮CCH2Ph)(PiPr3)]BF4 (12) and [Os(η 5-C5H4CH3)(GePh3){⋮CCH(CH3)Ph}(PiPr3)]BF4 (13).

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Section: Introductionmentioning

confidence: 61%

Influence of the Group 14 Element on the Deprotonation of OsH(η⁵-C₅H₅)(C⋮CPh)(EPh₃)(PⁱPr₃) (E = Si, Ge): Two Different Organometallic Chemistries

2001

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“…Knowing that P−O scission is facile in PONNOP, [19,20] we hypothesised that the mechanism likely involves nucleophilic attack of a PONNO − naphthyridinolate anion (generated in the presence of NiBr 2 or adventitious water) on an intact phosphinite group, templated by Ni coordination. Inter‐ [53–55] or intramolecular [48,56,57] attack of an O − , N − or F − nucleophile at a coordinated P III ligand is a common method for synthesising metallophosphoranes [41] . Ni templation is hypothesised to be essential for promoting formation of the PONNOPONNO macrocycle.…”

Section: Resultsmentioning

confidence: 99%

Bimetallic Nickel Complexes Supported by a Planar Macrocyclic Diphosphoranide Ligand

Delaney

Doan

et al. 2023

Chemistry A European J

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Metal-metal cooperativity is emerging as an important strategy in catalysis. This requires appropriate ligand scaffolds that can support two metals in close proximity. Here we report nickel-promoted formation of a dinucleating planar macrocyclic ligand that can support bimetallic dinickel(II) and dinickel(I) complexes. Reaction outcomes can be tuned by variation of the substituents and reaction conditions to favour dinucleating macrocyclic, mononucleating macrocyclic or conventional pincer architectures.

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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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Phosphorane Migration from Ruthenium to the Cyclopentadienyl Ring

Cited by 15 publications

References 18 publications

Influence of the Group 14 Element on the Deprotonation of OsH(η⁵-C₅H₅)(C⋮CPh)(EPh₃)(PⁱPr₃) (E = Si, Ge): Two Different Organometallic Chemistries

Influence of the Group 14 Element on the Deprotonation of OsH(η⁵-C₅H₅)(C⋮CPh)(EPh₃)(PⁱPr₃) (E = Si, Ge): Two Different Organometallic Chemistries

Bimetallic Nickel Complexes Supported by a Planar Macrocyclic Diphosphoranide Ligand

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

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Phosphorane Migration from Ruthenium to the Cyclopentadienyl Ring

Cited by 15 publications

References 18 publications

Influence of the Group 14 Element on the Deprotonation of OsH(η5-C5H5)(C⋮CPh)(EPh3)(PiPr3) (E = Si, Ge): Two Different Organometallic Chemistries

Influence of the Group 14 Element on the Deprotonation of OsH(η5-C5H5)(C⋮CPh)(EPh3)(PiPr3) (E = Si, Ge): Two Different Organometallic Chemistries

Bimetallic Nickel Complexes Supported by a Planar Macrocyclic Diphosphoranide Ligand

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

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Influence of the Group 14 Element on the Deprotonation of OsH(η⁵-C₅H₅)(C⋮CPh)(EPh₃)(PⁱPr₃) (E = Si, Ge): Two Different Organometallic Chemistries

Influence of the Group 14 Element on the Deprotonation of OsH(η⁵-C₅H₅)(C⋮CPh)(EPh₃)(PⁱPr₃) (E = Si, Ge): Two Different Organometallic Chemistries