| The reactivity of the unusual 14 electron compound (PNP tBu)RuCl (PNPtBu= N(SiMe2CH2P( tBu2))2), having square planar geometry and a triplet ground state, and some of its derivatives will be discussed. Many olefinic substrates will be tested, beginning with simple olefins and systematically working through more sophisticated olefins and alkynes. The main goal in this area of work is to evaluate the ability of this molecule to oxidatively add vinylic, allylic, and acetylenic C-H, C-C, and C-F bonds, a key step in any olefin polymerization. This molecule also reacts with PhN3 to give the salt composed of (PNPtBu)Ru(NPh)+ and (PNP tBu)RuCl3-, together with equimolar (PNP tBu)Ru(NPh). The contrast among these results and those with Fe, Co, and Ni is used to deduce what conditions favor N2 loss and oxidative incorporation of the NPh fragment from PhN3 into a metal complex and its location of incorporation. Study of the effect of both vertical and horizontal periodic trends helps to define the influence of available d orbitals and metal/phosphine bond lability for this reaction.;The generation of derivatives of (PNPtBu)RuCl, through routes of anion exchange and silyl transfer reagents, that have been synthesized are a handful of new four coordinate, planar, 14-electron compounds. The surprising nature of these new derivatives is discussed as well as their differing reactivity versus the parent chloride, specifically their behavior towards solvent, and their reactivity with N2. DFT studies of these new 4 coordinate compounds, and some compounds that were unable to be either isolated or synthesized will be included. Also, an unprecedented terminal ruthenium nitride was synthesized from azidotrimethylsilane and (PNPtBu)RuCl, and its characterization and reactivity are also discussed. Also discussed is the high yield reaction chemistry of this new terminal nitride which shows the ability of this molecule to react with (i) small electrophiles H+ and Me+, from Triflic acid and methyl triflate, and (ii) two different nitrogen oxides, one a radical (NO) and the other an even-electron species (N2O). |
