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Title: Direct lanthanide-transition metal interactions: Synthesis of (NH{sub 3}){sub 2}YbFe(CO){sub 4} and crystal structures of ([(CH{sub 3}CN){sub 3}YbFe(CO){sub 4}]{sub 2}{center_dot}CH{sub 3}CN){infinity} and [(CH{sub 3}CN){sub 3}YbFe(CO){sub 4}]{sub infinity}

Journal Article · · Inorganic Chemistry
DOI:https://doi.org/10.1021/ic9515113· OSTI ID:274271

The heterometallic complex (NH{sub 3}){sub 2}YbFe(CO){sub 4} was prepared from the reduction of Fe{sub 3}(CO){sub 12} by Yb in liquid ammonia. Ammonia was displaced from (NH{sub 3}){sub 2}YbFe(CO){sub 4} by acetonitrile in acetonitrile solution, and the crystalline compounds ([(CH{sub 3}CN){sub 3}YbFe(CO){sub 4}]{sub 2}{center_dot}CH{sub 3}CN){sub infinity} showed that it is a ladder polymer with direct Yb-Fe bonds. In the present study, an X-ray crystal structure analysis also showed that [(CH{sub 3}CN){sub 3}YbFe(CO){sub 4}]{sub infinity} showed that it is a ladder polymer with direct Yb-Fe bonds. In the present study, an X-ray crystal structure analysis also showed that [(CH{sub 3}CN){sub 3}YbFe(CO){sub 4}]{sub infinity} is a sheetlike array with direct Yb-Fe bonds. Electrical conductivity measurements in acetonitrile show that these acetonitrile complexes are partially dissociated into ionic species. IR and NMR spectra of the solutions reveal the presence of [HFe(CO){sub 4}]{sup {minus}}. However, upon recrystallization, the acetonitrile complexes show no evidence for the presence of [HFe(CO){sub 4}]{sup {minus}}. However, upon recrystallization, the acetonitrile complexes show no evidence for the presence of [HFe(CO){sub 4}]{sup {minus}} on the basis of their IR spectra. The solid state MAS {sup 2}H NMR spectra of deuterated acetonitrile complexes give no evidence for [{sup 2}HFe(CO){sub 4}]{sup {minus}}. It appears that the rupture of the Yb-Fe bond could occur in solution to generate the ion pair [L{sub n}Yb]{sup 2+}[Fe(CO){sub 4}]{sup 2{minus}}, but then the highly basic [Fe(CO){sub 4}]{sup 2{minus}} anion could abstract a proton from a coordinated acetonitrile ligand to form [HF3(CO){sub 4}]{sup {minus}}. However, upon crystallization, the proton could be transferred back to the ligand, which results in the neutral polymeric species.

OSTI ID:
274271
Journal Information:
Inorganic Chemistry, Vol. 35, Issue 13; Other Information: PBD: 19 Jun 1996
Country of Publication:
United States
Language:
English

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