(Pentamethylcyclopentadienyl)molybdenum(IV) Chloride. Synthesis, Structure, and Properties

Fatima Abugideiri (1) , Gregory Brewer (2) , Jahanvi Desai (1) , John Gordon (1) , Rinaldo Poli (1)

1 University of Maryland [College Park]
2 Catholic University of America

Three different syntheses of trichloro(pentamethylcyclopentadienyl)molybdenum(IY) are described, i.e. (i) thermal decarbonylation of Cp*MoCl3(CO)2, (ii) reduction of Cp*MoCl4, and (iii) chlorination of [Cp*MoCl2)2. A fourth route (conproportionation of [Cp*MoCl2]2 and Cp*MoCl4) has been investigated by 1H-NMR. The product has a dinuclear, dichloro-bridged structure with a four-legged piano stool geometry around each metal atom; the two piano stools have a mutual anti arrangement and the two metals are 3.888(1) A from each other, indicating the absence of a direct metal-metal bonding interaction. Crystal data: monoclinic, space group P2i /n, a= 8.424(1) A, b = 13.323(4) A, c = 11.266(2) A, f3 = 93.87(1)0, V = 1261.6(8) A3, Z = 2, R = 0.038, R., = 0.051 for 127 parameters and 1350 observed reflections with F02 > 3u(F02). The temperature dependent magnetic moment of the material could be fit to the sum of two Bleany-Bowers equations. [Cp*MoCl3]2 reacts readily with CO, Cl-, and PMe3 to afford Cp*MoCl3(CO)2, [Cp*MoCI4]- and Cp*MoCl3(PMe3), respectively, while the reaction with 1,2-bis(diphenylphosphino)ethane (dppe) affords the reduction product Cp*MoCl2(dppe).

Domaines: Chimie de coordination; Cristallographie

Fatima Abugideiri, Gregory Brewer, Jahanvi Desai, John Gordon, Rinaldo Poli. (Pentamethylcyclopentadienyl)molybdenum(IV) Chloride. Synthesis, Structure, and Properties. Inorganic Chemistry, 1994, 33 (17), pp.3745-3751. ⟨10.1021/ic00095a018⟩. ⟨hal-03533029⟩