Metal-ligand Multiple Bonds in Nickel Complexes Supported by Chelating Bisphosphine Ligands

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ProQuest, 2009 - 275 pages
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Chapter 4 describes our efforts to synthesize a nickel(III) carbyne species. A nickel carbene, (dtbpe)Ni=CH(dmp), was obtained from the photolysis of the corresponding (dtbpe)Ni{eta2-N2CH(dmp)} and structurally characterized. Oxidation of the Ni(II) carbene, (dtbpe)Ni=CH(dmp), takes place with rearrangement of the Ni coordination environment, involving phosphine migration to the carbene carbon in the expected Ni(III) intermediate species, [(dtbpe)Ni=CH(dmp)+]. These results were explained with the aid of DFT calculations, which indicate that in the case of the imido complex (dtbpe)Ni=N(dmp) the HOMO is an antibonding orbital, while in the case of the carbene (dtbpe)Ni=CH(dmp) it is a bonding one, making the electron removal process difficult.
 

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Contents

NiSi Complexes
7
A new NiIII Imide Complex
54
A New NiII Carbene
96
PeriSubstituted Naphthalene as a Rigid Backbone
127
A Experimental Details
156
A6 Experimental Procedures for Chapter 4
169
A7 Experimental Procedure for Chapter 5
175
A8 References
184
B Crystallographic Data
186
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