Date of Award

Winter 1993

Abstract

Substitution of triphosphoxane rings on metal complexes containing labile ligands, M(CO)$\sb4$NBD and $\rm MX\sb2L\sb2$ (X = Cl, Br, I; L = DME, THF, NBD) and thermal reactions of bis(dialkylamino)phosphine oxides with metal hexacarbonyls yielded the tri-, tetra-, and pentaphosphoxane ring complexes cis-$\rm M(CO)\sb4\lbrack R\sb2NPO\rbrack\sb3,$ cis-$\rm M(CO)\sb4\lbrack R\sb2NPO\rbrack\sb4,$ cis-$\rm M\sb2(CO)\sb8\lbrack R\sb2NPO\rbrack\sb4,$ cis-$\rm M\sb2(CO)\sb7\lbrack R\sb2NPO\rbrack\sb5,$ cis-$\rm MX\sb2\lbrack R\sb2NPO\rbrack\sb4,$ and cis-$\rm MX\sb2\lbrack R\sb2NPO\rbrack\sb5$ as the isolated products. The P$\sb4$O$\sb4$ rings in metal tetraphosphoxane complexes appear in six coordination modes including the 1,3-chelating, 1,5-chelating boat-boat, boat-chair conformation, 1,3,5,7-chelating boat-boat cage mode, twist-boat mode, and 1,3,5-tridentate mode bridging two metals. A novel Ni(O)-cage complex $\rm Ni\sb2(CO)\sb4\lbrack Cy\sb2NPO\rbrack\sb4$ was synthesized serendipitously from thermal reaction of $\rm Fe\sb2(CO)\sb{g}$ with $\rm NiBr\sb2\lbrack Cy\sb2NPO\rbrack\sb4$ in toluene. Several bimetallic complexes were synthesized from the reaction of monometallic polyphosphoxane complexes with suitable metal precursors.

Some side reactions accompanied the above reactions giving metal complexes with new ring skeletons, $\rm Fe(CO)\sb4\{\sp{i}Pr\sb2NP\lbrack OP(O)\sp{i}Pr\sb2N\rbrack\sb2PN\sp{i}Pr\sb2\},$ and a tungsten complex $\rm W(CO)\sb3\lbrack R\sb2NPO\rbrack\sb4W(CO)\sb3.$ The novel hexaphosphoxane $\rm Cr\sb2P\sb6O\sb6$ complex was produced by a stepwise addition of R $-$ P = O units in the thermal reaction of $\rm Cr\sb2(CO)\sb7\lbrack DMP$-PO) $\sb5$ with bis(dimethylpiperidino)phosphine oxide.

Document Type

Dissertation

First Advisor

Edward Wong

Department or Program

Chemistry

Degree Name

Doctor of Philosophy

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