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• W2064004505 abstract "EPR spectra are reported for four metal complexes of 2,3-bis(diphenylphosphino)maleic anhydride (BMA), [Co2(PhCCR)(CO)4(η-BMA)]-, R = Ph, H, [Co2(PhCCPh)(CO)4(μ-BMA)]-, and [PhCW(CO)2(BMA)Cl]-, as well as the radical anions, [BMA]- and [BPCD]-, BPCD = 4,5-bis(diphenylphosphino)cyclopentene-1,3-dione. At room temperature, all spectra are 1:2:1 triplets due to hyperfine coupling to two equivalent 31P nuclei with coupling to two equivalent 1H nuclei for [BPCD]- and unresolved coupling to one or two 59Co nuclei for the Co complexes with chelating or bridging BMA, respectively. The 31P couplings are temperature dependent, ca. −3 and −13 mG K-1 for the metal complexes and ligand radical anions, respectively. At low temperature, the spectrum of [BMA]- shows the presence of symmetric and asymmetric PPh2 rotational conformers, related by the thermodynamic parameters ΔH° = −0.8 ± 0.2 kJ mol-1 and ΔS° = 4 ± 1 J mol-1 K-1 and interconverted with activation parameters ΔH⧧ = 18.2 ± 0.4 kJ mol-1, ΔS⧧ = −30 ± 2 J mol-1 K-1. The temperature dependence of the 31P couplings is explained by a negative spin-polarization contribution to 〈aP〉 and a positive contribution due to P 3s character; the latter increases with the asymmetry of the PPh2 conformations. The range of conformations accessible to the metal complexes is less than for the ligand radical anions, and accordingly the temperature dependence is significantly smaller." @default.
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• W2064004505 date "1998-09-01" @default.
• W2064004505 modified "2023-09-26" @default.
• W2064004505 title "An EPR Study of 2,3-Bis(diphenylphosphino)maleic Anhydride (BMA) Complexes and the BMA Radical Anion" @default.
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• W2064004505 doi "https://doi.org/10.1021/ic980581h" @default.
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