Matches in SemOpenAlex for { <https://semopenalex.org/work/W2010167211> ?p ?o ?g. }
- W2010167211 endingPage "526" @default.
- W2010167211 startingPage "511" @default.
- W2010167211 abstract "Rapid reactions occur between [OsVI(tpy)(Cl)2(N)]X (X = PF6−, Cl−, tpy = 2,2′:6′,2″-terpyridine) and aryl or alkyl phosphi nes (PPh3, PPh2Me, PPhMe2, PMe3 and PEt3) in CH2Cl2 or CH3CN to give [OsIV(tpy)(Cl)2(NPPh3)]+ and its analogs. The reaction between trans-[OsVI(tpy)(Cl)2(N)]+ and PPh3 in CH3CN occurs with a 1:1 stoichiometry and a rate law first order in both PPh3 and OsVI with k(CH3CN, 25°C) = 1.36 ± 0.08 × 104 M− s−1. The products are best formulated as paramagnetic d4 phosphoraniminato complexes of OsIV based on a room temperature magnetic moment of 1.8 μB for trans-[OsIV(tpy)(Cl)2(NPPh3)](PF6), contact shifted 1H NMR spectra and UV-Vis and near-IR spectra. In the crystal structures of trans-[OsIV(tpy)(Cl)2( NPPh3)](PF6)·CH3CN (monoclinic, P21/n with a = 13.384(5) Å, b = 15.222(7) Å, c = 17.717(6) Å, β = 103.10(3)°, V = 3516(2) Å3, Z = 4, Rw = 3.40, Rw = 3.50) and cis-[OsIV(tpy)(Cl)2(NPPh2Me)]-(PF6)·CH3CN (monoclinic, P21/c, with a = 10.6348(2) Å, b = 15.146(9) ÅA, c = 20.876(6) Å, β = 97.47(1)°, V = 3334(2) Å3, Z = 4, R = 4.00, Rw = 4.90), the long Os-N(P) bond lengths (2.093(5) and 2.061(6) Å), acute Os-N-P angles (132.4(3) and 132.2(4)°), and absence of a significant structural trans effect rule out significant Os-N multiple bonding. From cyclic voltammetric measurements, chemically reversible OsV/IV and OsIV/III couples occur for trans-[OsIV(tpy)(Cl)2(NPPh3)](PF6) in CH3CN at +0.92 V (OsV/IV) and −0.27 V (OsIV/III) versus SSCE. Chemical or electrochemical reduction of trans-[OsIV(tpy)(Cl)2(NPPh3)](PF6) gives isolable trans-OsIII(tpy)(Cl)2(NPPh3). One-electron oxidation to OsV followed by intermolecular disproportionation and PPh3 group transfer gives [OsVI(tpy)Cl2(N)]+, [OSIII(tpy)(Cl)2(CH3CN)]+ and [Ph3=N=PPh3]+ (PPN+). trans-[OsIV(tpy)(Cl)2(NPPh3)](PF6) undergoes reaction with a second phosphine under reflux to give PPN+ derivatives and OsII(tpy)(Cl)2(CH3CN) in CH3CN or OsII(tpy)(Cl)2(PR3) in CH2Cl2. This demonstrates that the OsVI nitrido complex can undergo a net four-electron change by a combination of atom and group transfers." @default.
- W2010167211 created "2016-06-24" @default.
- W2010167211 creator A5004681512 @default.
- W2010167211 creator A5039908353 @default.
- W2010167211 creator A5051913055 @default.
- W2010167211 creator A5061302621 @default.
- W2010167211 creator A5089516413 @default.
- W2010167211 creator A5089721195 @default.
- W2010167211 date "1998-04-01" @default.
- W2010167211 modified "2023-10-16" @default.
- W2010167211 title "Nitrogen atom transfer and redox chemistry of terpyridyl phosphoraniminato complexes of osmium (IV)" @default.
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