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2ₛ + 2ₛ Reactions at Transition Metals


Steigerwald, Michael Louis (1984) 2ₛ + 2ₛ Reactions at Transition Metals. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/S0HZ-TF05.


A study of the suprafacial 2 + 2 reaction at transition metal centers is presented. It is demonstrated that this reaction is allowed and proceeds with a low activation energy if the reacting transition metal-to-substituent bond is covalent, nonpolar, and has a large component at transition nickel d-orbital character. These chains are evinced by examination of 2s + 2s reactions at M-H bonds. Those systems in which M can use d orbitals show lower barriers to the 2s + 2s reaction than those in which M cannot use d orbitals.

The importance of the electronic structure of the metal-to-substituent bond is highlighted by a study of dichorotitanacyclopropane. This molecule, being a metallacyclopropane, can undergo 2s + 2s reactions which one unavailable to a simple olefin.

Studies concerning the importance of 2s + 2s reactivity in the organic chemistry of nickel, and in the Ziegler-Natta polymerization of simple olefins are presented.

It is suggested that the principle of maximum bonding (the Woodward-Hoffmann rules) implies the conservation of transition metal covalency in low-energy catalytic cycles.

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):
  • Gray, Harry B.
Thesis Committee:
  • Goddard, William A., III (chair)
  • Grubbs, Robert H.
  • Bercaw, John E.
  • Dougherty, Dennis A.
  • Gray, Harry B.
Defense Date:12 September 1983
Funding AgencyGrant Number
Record Number:CaltechETD:etd-01032007-142600
Persistent URL:
Related URLs:
URLURL TypeDescription adapted for Chapter 7.I.
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:12
Deposited By: Imported from ETD-db
Deposited On:03 Jan 2007
Last Modified:21 Dec 2019 02:01

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PDF (Steigerwald_ml_1984.pdf) - Final Version
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