Date of Award

Winter 1993

Project Type

Dissertation

Program or Major

Chemistry

Degree Name

Doctor of Philosophy

First Advisor

Edward Wong

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.

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