Detection of 1 H -Triphosphirene ( c -HP 3 ) and 2-Triphosphenylidene (HP 3 ): The Isovalent Counterparts of 1 H -Triazirine ( c -HN 3 ) and Hydrazoic Acid (HN 3 )
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The reduction potentials (reported vs. Fc + /Fc) for a series of Cp′ 3 Ln complexes (Cp′ = C 5 H 4 SiMe 3 , Ln = lanthanide) were determined via electrochemistry in THF with [ n Bu 4 N][BPh 4 ] as the supporting electrolyte. The Ln( iii )/Ln( ii ) reduction potentials for Ln = Eu, Yb, Sm, and Tm (−1.07 to −2.83 V) follow the expected trend for stability of 4f 7 , 4f 14 , 4f 6 , and 4f 13 Ln( ii ) ions, respectively. The reduction potentials for Ln = Pr, Nd, Gd, Tb, Dy, Ho, Er, and Lu, that form 4f n 5d 1 Ln( ii ) ions ( n = 2–14), fall in a narrow range of −2.95 V to −3.14 V. Only cathodic events were observed for La and Ce at −3.36 V and −3.43 V, respectively. The reduction potentials of the Ln( ii ) compounds [K(2.2.2-cryptand)][Cp′ 3 Ln] (Ln = Pr, Sm, Eu) match those of the Cp′ 3 Ln complexes. The reduction potentials of nine (C 5 Me 4 H) 3 Ln complexes were also studied and found to be 0.05–0.24 V more negative than those of the Cp′ 3 Ln compounds.more » « less
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Abstract We present the spectroscopic characterization of cyclopropenethione in the laboratory and detect it in space using the Green Bank Telescope Observations of TMC-1: Hunting Aromatic Molecules survey. The detection of this molecule—the missing link in understanding the C3H2S isomeric family in TMC-1—completes the detection of all three low-energy isomers of C3H2S, as both CH2CCS and HCCCHS have been previously detected in this source. The total column density of this molecule (NTof cm−2at an excitation temperature of K) is smaller than both CH2CCS and HCCCHS and follows nicely the relative dipole principle (RDP), a kinetic rule of thumb for predicting isomer abundances that suggests that, all other chemistry among a family of isomers being the same, the member with the smallest dipole (μ) should be the most abundant. The RDP now holds for the astronomical abundance ratios of both the S-bearing and O-bearing counterparts observed in TMC-1; however, CH2CCO continues to elude detection in any astronomical source.more » « less
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