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Creators/Authors contains: "Jordan, Aldo M."

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  1. When irradiated with blue light in the presence of a Lewis base (L), [CpW(CO) 3 ] 2 undergoes metal–metal bond cleavage followed by a disproportionation reaction to form [CpW(CO) 3 L] + and [CpW(CO) 3 ] − . Here, we show that in the presence of pyridinium tetrafluoroborate, [CpW(CO) 3 ] − reacts further to form a metal hydride complex CpW(CO) 3 H. The rection was monitored through in situ photo 1 H NMR spectroscopy experiments and the mechanism of light-driven hydride formation was investigated by determining quantum yields of formation. Quantum yields of formation of CpW(CO) 3 H correlate with I −1/2 (I = photon flux on our sample tube), indicating that the net disproportionation of [CpW(CO) 3 ] 2 to form the hydride precursor [CpW(CO) 3 ] − occurs primarily through a radical chain mechanism. 
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  2. A new diarylmido-based pincer proto ligand ( iPrPNHSbPh ) with one –PPr i 2 and one –SbPh 2 side donor has been synthesized. Three complexes of its amido form were prepared using standard metalation techniques: ( iPrPNSbPh ) PdCl , ( iPrPNSbPh ) RhCO , and ( iPrPNSbPh ) Ir(COE) , where COE = cis -cyclooctene. These complexes were compared with their previously reported analogs incorporating a –PPh 2 side donor in place of –SbPh 2 . The –SbPh 2 donor arm is less donating towards the metal and is less strongly trans -influencing, based on the structural and IR spectroscopic analysis of the Rh complexes. The redox potential of the Pd complexes is only marginally affected by the change from –PPh 2 to –SbPh 2 . (iPrPNSbPh)Ir(COE) proved to be a slower and less selective catalyst in the dehydrogenative borylation of terminal alkynes (DHBTA) than its –PPh 2 analog. 
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