Carbene derivatives of molybdenum and tungsten containing metal-metal bonds

Dean, Walter K.; Graham, W. A. G.

doi:10.1021/ic50171a020

Cited by 51 publications

(9 citation statements)

References 8 publications

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“…Yield: 130 mg (72%). 1 H NMR (300 MHz, C6D6, 293 K): δ 7.90-6.80 (20 H,Ph);4 H, signals of η 5 -C5H4); 1.94 (m, 3 H, PCH); 0.86 (dd, 9 H, PCHCH3, 3 JHP ) 14.1 Hz, 3 JHH ) 7.2 Hz); 0.84 (dd, 9 H, PCHCH3, 3 JHP ) 14.1 Hz, 3 JHH ) 7.2 Hz); -14.15 (d, 1 H, OsH, 2 JHP ) 29. 1 Hz).…”

Section: Methodsunclassified

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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

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: Methodsunclassified

“…1999, 193-195, 977. tungsten, 4 rhenium, 5 iron, 6 and ruthenium 7 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: 99%

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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“…It has been reported for η 5 -cyclopentadienyl (Cp)-containing complexes that one of the ligands undergoes base-induced migration to the Cp ring (eq 1). The first example of this type of migration reaction was reported by Dean and Graham in 1977 for Cp(CO) 3 M(GePh 3 ) (M = Mo, W) . Since then, several types of ligand have been illustrated to migrate from a transition metal to the Cp ring: acyl, alkoxycarbonyl,15c formyl, 15e,f silyl, germyl, stannyl, plumbyl, hydride, and phosphonate 19 migration.…”

Section: Introductionmentioning

confidence: 99%

Migration Reaction of a Hypervalent Fragment: Base-Induced Migration of a Phosphorane Fragment from Iron to the Cyclopentadienyl Ring in Cp(CO)₂Fe{P(OC₆H₄Y)(OC₆H₄Z)} (Y, Z = NMe, NH, O)

et al. 1998

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Iron phosphorane complexes, (Y, Z = NMe, O), react with lithium diisopropylamide (LDA) and then MeI to give showing the first example of migration of a hypervalent phosphorus fragment. The structure of one of the migration products, was determined by X-ray analysis. Spectroscopic monitoring of the migration reaction suggests that the reaction is initiated by a proton abstraction on the Cp ring by LDA, followed by migration of the phosphorane fragment to the Cp ring to give which is converted into by the treatment of alkyl halide. The reaction of containing two NH groups with LDA proceeds first with NH proton abstraction to give and then with Cp proton abstraction followed by phosphorane migration to give The addition of MeI finally led to the isolation of and

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“…The anion-induced migration reaction of a ligand from a metal atom to a neighboring cyclopentadienyl carbon atom has been known for about 20 years. 1 Such a reaction is characterized by its intramolecular nature and is generally initiated by a deprotonation of the cyclopentadienyl ring causing a group to migrate from a metal to a cyclopentadienyl ring, followed by quenching of the anion produced. The known examples include acyl, 2,3 ester, 3 hydride, 4 and heteroatom-containing (Si, 5 Ge, 6 Sn 6 and P 7 ) groups, in conjunction with Group 6 to Group 8 transitionmetal elements.…”

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confidence: 99%

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

Liu¹,

Chang²,

Wen³

1998

J. Chem. Soc., Dalton Trans.

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Carbene derivatives of molybdenum and tungsten containing metal-metal bonds

Cited by 51 publications

References 8 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

Migration Reaction of a Hypervalent Fragment: Base-Induced Migration of a Phosphorane Fragment from Iron to the Cyclopentadienyl Ring in Cp(CO)₂Fe{P(OC₆H₄Y)(OC₆H₄Z)} (Y, Z = NMe, NH, O)

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

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Carbene derivatives of molybdenum and tungsten containing metal-metal bonds

Cited by 51 publications

References 8 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

Migration Reaction of a Hypervalent Fragment: Base-Induced Migration of a Phosphorane Fragment from Iron to the Cyclopentadienyl Ring in Cp(CO)2Fe{P(OC6H4Y)(OC6H4Z)} (Y, Z = NMe, NH, O)

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

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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

Migration Reaction of a Hypervalent Fragment: Base-Induced Migration of a Phosphorane Fragment from Iron to the Cyclopentadienyl Ring in Cp(CO)₂Fe{P(OC₆H₄Y)(OC₆H₄Z)} (Y, Z = NMe, NH, O)