Insertion and [beta]-hydride elimination reactions of ruthenium/zirconium complexes containing C[sub 2] bridges with bond orders of 1, 2, and 3

Journal Article · Mon Nov 30 23:00:00 EST 1992 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00060a051· OSTI ID:6443429

Lemke, F R; Bullock, R M ^[1]

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1. Brookhaven National Lab., Upton, NY (United States)

Carbon dioxide inserts into the Zr-C bond of Cp(PMe[sub 3])[sub 2]RuCH[double bond]CHZrClCp[sub 2], producing the carboxylate complex Cp(PMe[sub 3])[sub 2]RuCH[double bond]CHCO[sub 2]ZrClCp[sub 2]. An [eta][sup 2]-iminoacyl insertion product, Cp(PMe[sub 3])[sub 2]Ru-C[triple bond]C-C(N[sub t]Bu)ZrClCp[sub 2], results from insertion of [sup t]BuNC into the Zr-C bond of the dimetalloalkyne complex Cp(PMe[sub 3])[sub 2]Ru-C[triple bond]C-ZrClCp[sub 2]. The reaction of Cp(PMe[sub 3])[sub 2]RuCH[sub 2]CH[sub 2]ZrClCp[sub 2] with high concentrations of [sup t]BuNC also produces an [eta][sup 2]-iminoacyl insertion product, Cp(PMe[sub 3])[sub 2]RuCH[sub 2]CH[sub 2]C(N[sup t]Bu)ZrClCp[sub 2]. At low concentrations of [sup t]BuNC, a competing reaction is [beta]-hydride elimination from Cp(PMe[sub 3])[sub 2]RuCH[sub 2]CH[sub 2]ZrClCp[sub 2] to give Cp(PMe[sub 3])[sub 2]RuCH[double bond]CH[sub 2] and Cp[sub 2]Zr(H)Cl, which is trapped by [sup t]BuNC under these conditions to give Cp[sub 2]ZrCl([eta][sup 2]-[sup t]BuN[double bond]CH). The reaction of benzophenone with Cp(PMe[sub 3])[sub 2]RuCH[sub 2]CH[sub 2]ZrClCp[sub 2] gives the insertion product Cp(PMe[sub 3])[sub 2]RuCH[sub 2]CH[sub 2]CPh[sub 2]OZrClCp[sub 2]. [beta]-Hydride elimination is also observed from Cp(PMe[sub 3])[sub 2]RuCH[double bond]CHZrClCp[sub 2]; in the presence of excess [sup n]BuC[triple bond]CH, the products are Cp(PMe[sub 3])[sub 2]Ru-C[triple bond]C-H and the zirconium vinyl complex Cp[sub 2]Zr(Cl)CH[double bond]CH[sup n]Bu. 25 refs.

• DOE Contract Number: AC02-76CH00016
• OSTI ID: 6443429
• Journal Information: Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 11:12; ISSN 0276-7333; ISSN ORGND7
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BENZOPHENONE
CARBON COMPOUNDS
CARBON DIOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
HYDRIDES
HYDROGEN COMPOUNDS
KETONES
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
RUTHENIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES
ZIRCONIUM COMPLEXES