Synthesis, Characterization, and Reactivity of the Heterometallic Dinuclear μ-PH2 and μ-PPhH Complexes FeMn(CO)8(μ-PH2) and FeMn(CO)8(μ-PPhH)Organometallics (2010)
Deprotonation of Fe(CO)4PRH2 and treatment with Mn(CO)5Br afforded the dinuclear complexes FeMn(CO)8(μ-PRH) (1a, R = H; 1b, R = Ph), which contain the relatively rare μ-PH2and μ-PPhH functionalities. The heterometallic nature of these complexes was confirmed by mass spectrometry, and the molecular structures of 1a and 1b were determined by X-ray diffraction experiments. Deprotonation of 1b and subsequent addition of Mn(CO)5Br or AuPPh3Cl yielded the trinuclear complexes FeMn(CO)8[μ-PPh(Mn(CO)5)] (3a) and FeMn(CO)8[μ-PPh(AuPPh3)] (3b), both of which were characterized structurally and spectroscopically. Deprotonation of 1a at room temperature resulted in rapid coupling of the deprotonated product [2a]− with neutral 1a to form M+[FeMn(CO)8(μ3-PH)Mn(CO)4(μ-PH2)Fe(CO)4]− (M+−) (M+ = Li+, Na+, K+), the formation of which was observed using in situinfrared spectroscopy. M+− was found to decompose upon solvent removal, and the structure of − was elucidated by examination of spectroscopic data. The 1H NMR spectrum of - was characterized by first-order [ABMX] and [AMX] spin systems, and ESI-MS data confirmed that− was formed by direct coupling of [2a]− with 1a without concomitant fragmentation or loss of CO ligands. Deprotonation of 1a at lower temperatures slowed the coupling process, allowing for the metalation of the monomeric anion [2a]− by treatment with AuPPh3Cl, the product of which was found to decompose gradually in solution and rapidly upon concentration.
Publication DateOctober 25, 2010
Citation InformationAdam C. Colson and Kenton H. Whitmire. "Synthesis, Characterization, and Reactivity of the Heterometallic Dinuclear μ-PH2 and μ-PPhH Complexes FeMn(CO)8(μ-PH2) and FeMn(CO)8(μ-PPhH)" Organometallics Vol. 29 Iss. 20 (2010) p. 4417 - 4646
Available at: http://works.bepress.com/adam-colson/5/