Synthesis and Characterization of Transition Metal Silyl Complexes and Phthalocyanine and Phthalocyanine-Like Compounds.

Part I. Transition Metal Silyl Complexes. In order to investigate transition metal silyl systems, a series of iridium silyl compounds have been resynthesized and further characterized. These systems were of the general formula rm IrHY(P(CH_3)_3) _3SiRR^'_2 (where Y = H, D or Cl) and were found to exclusively have their phosphines in a fac arrangement. A series of platinum silyl four membered ring compounds with an unusual Si-Si interaction were resynthesized and further characterized. The characterization of these compounds, although somewhat complicated, gave support for a mu_2-eta _2-disilene bonding description for the Si -Si interaction. The reaction chemistry of these compounds was also investigated and was also found to support the mu_2-eta_2 -disilene bonding description. Additionally, the ability for these compounds to act as catalysts or catalyst precursors for the dehydrocoupling of silanes has been investigated. Finally the complete X-ray crystal structure determinations for the compounds trans-PtClH(P(rm C_2H _5)_3)_2,{it fac} -IrH_2(P(CH_3)_3)_3Si(C _6H_5)_3,{it trans} -PdCl_2(P(C_6H_ {11})_3)_2 and Mo(CO) _5(NC_5H_5) have been carried out. Part II. Phthalocyanine and Phthalocyanine-Like Compounds. The boron subphthalocyanines BsubPcCl, BsubPcBr, BsubPcOMe, BsubPcOEt, BsubPcOSi(n-rm C_6H _{13})_3, BsubPcN(i- rm C_3H_7)_2, BsubPc -i-rm C_4H_9, and BsubPc(t -Bu)_3Cl have been synthesized and characterized. Their chemical, physical and spectroscopic properties have been found to be closely related to those of the phthalocyanines. Likewise, the boron subnaphthalocyanines BsubNcCl and BsubNcN(i-rm C_3H_7) _2 have been synthesized and characterized. The chemical, physical and spectroscopic properties of these two compounds have been found to be closely related to those of the naphthalocyanines. The subphthalocyanine-phthalocyanine ring expansion reaction has been further investigated and found to have wide generality. Unsymmetrically substituted phthalocyanines, including a push-pull phthalocyanine, have been made by this reaction and have been characterized. By other chemistry a fused-ring phthalocyanine has been resynthesized and further characterized. X-ray crystal structures of BsubPc-i- {rm C_4H_9cdot{~ }0.4} n-rm C_6H _{14} and GePc (OSi(n- rm C_6H_{13})_3] _2 have been determined. As expected, the ring of the former is conically shaped while that of the latter is planar. The siloxy groups of the latter are flattened.