Preparation of cis-[MoI4(Ph2PCH2CH2PPh2)]− and structure of (THF)3Na(μ-I)3MoI(Ph2PCH2CH2PPh2) with a new coordination environment around sodium

Sundeep Mattamana (1) , Rinaldo Poli (1)

1 University of Maryland [College Park]

The complex cis-[MoI4(dppe)]- is obtained in good yields from trans-[MoI4(THF)2]- and dppe (dppe=1,2-bis(diphenylphosphino)ethane) or directly from the interaction of MoI3(THF)3, I- and dppe and has been isolated as the PPh4 and Na(THF)3 salts. The sodium salt has been characterized crystallographically: monoclinic P21/n, a = 12.790(2), b = 16.512(7), c=23.117(4) Å, β=103.65(1) °, V=4744(1) Å3, Dcalc= 1.84 g cm-3, Z=4, R=0.039 for 4485 independent observed reflections (Fo2⩾3σ (Fo2)). The structure features an octahedral coordination around both Na and Mo atoms in an overall face-sharing bioctahedral structure with the two metals being bridged by three iodide ligands. This is an unprecedented case of a structure containing an O3I 3 coordination for Na ions and iodide ligands bridging sodium with a transition metal. The 1H NMR properties of the complex are also examined in comparison to those of the MoI3(dppe)(THF) precursor.

Mots clés: Crystal structures; Molybdenum complexes; Iodide complexes; Diphosphine complexes; Sodium complexes

Domaines: Chimie de coordination; Cristallographie

Sundeep Mattamana, Rinaldo Poli. Preparation of cis-[MoI4(Ph2PCH2CH2PPh2)]− and structure of (THF)3Na(μ-I)3MoI(Ph2PCH2CH2PPh2) with a new coordination environment around sodium. Inorganica Chimica Acta, 1995, 229 (1-2), pp.55-60. ⟨10.1016/0020-1693(94)04226-L⟩. ⟨hal-03532498⟩