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Synthesis and Reactivity of Transition of Metal Homo- and Heterobinuclear Ketene Complexes


Ho, Suzzy Chen Hsi (1986) Synthesis and Reactivity of Transition of Metal Homo- and Heterobinuclear Ketene Complexes. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/bmj9-a007.


The rearrangement of β-phenyltitanacyclobutane (1) to α-phenyltitanacyclobutane (2) is shown through labeling experiments to proceed by a stepwise mechanism. Ring opening of 1 to the metalmethylidene species followed by readdition of styrene affords both complexes 1 and 2.

The reaction of titanacyclobutanes with oxidizing agents produces cyclopropanes in good yield. The stereochemistry of this reaction has been investigated using cis-2,3-dimethyltitanacyclobutane and trans-2-deutero-3-phenyltitanacyclobutane. By the use of 2H NMR, the stereochemistry of each step of the reaction has been determined.

The crystal and molecular structure of zirconaenolate anion Cp2Zr(η2-OCCH2-O,C)CH3Na•2 THE prepared by deprotonation of the corresponding acyl complex has been determined. The reactivity of this anion with electrophilic reagents is studied. Reaction with alkyl halides leads to C-substituted acyl complexes. Reaction with metal chlorides L2M(CH3)Cl leads to binuclear ketene complexes (Cp2ZrCH3)(µ-η2-OCCH2-O,C)-(MCH3L2) (M = Zr, Pt; L = Cp, phosphines). The mechanism for the formation of these complexes and their reactivities are discussed in detail.

The interaction of phosphonium and sulfoxonium ylides with acyl complexes of titanium and zirconium is examined. Reaction of Cp2Zr(COR)R' (R,R' = akyl, aryl) with CH23 and CH2SO(CH3)2 gives enolate complex Cp2Zr(OCR=CH2)R'. Treatment of titanocene chloro acyls with CH2SO(CH3)2 affords ketene complexes which react with excess ylides to give titanaoxacyclobutanes. The structure of titanaoxacyclobutane is determined by Dynamic NMR techniques. The zirconium chloro acyls react with CH2SO(CH3)2 to give mixtures of ketene and enolate complexes. Both react further with the ylides to yield zirconaoxacyclobutanes.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Dougherty, Dennis A. (advisor)
  • Grubbs, Robert H. (co-advisor)
Thesis Committee:
  • Dougherty, Dennis A. (chair)
  • Grubbs, Robert H.
  • Collins, Terrence J.
  • Bercaw, John E.
Defense Date:8 July 1985
Funding AgencyGrant Number
Standard Oil of OhioUNSPECIFIED
Record Number:CaltechTHESIS:04152019-104421637
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:11462
Deposited By: Mel Ray
Deposited On:15 Apr 2019 20:00
Last Modified:16 Apr 2021 22:59

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