Coordination solids derived from Cp*M(CN){sub 3}{sup {minus}} (M = Rh, Ir)

Journal Article · Mon May 15 04:00:00 EDT 2000 · Inorganic Chemistry

DOI:https://doi.org/10.1021/ic991037r· OSTI ID:20075874

Contakes, S M; Klausmeyer, K K; Rauchfuss, T B

Solutions of Rh{sub 2}(OAc){sub 4} and Et{sub 4}N[Cp*Ir(CN){sub 3}] react to afford crystals of the one-dimensional coordination solid {l_brace}Et{sub 4}N[Cp*Ir(CN){sub 3}][Rh{sub 2}(OAc){sub 4}]{r_brace}. This reaction is reversed by coordinating solvents such as MeCN. The structure of the polymer consists of helical anionic chains containing Rh{sub 2}(OAc){sub 4} units linked via two of the three CN ligands of Cp*Ir(CN){sub 3}{sup {minus}}. Use of the more Lewis acidic Rh{sub 2}(O{sub 2}CCF{sub 3}){sub 4} in place of Rh{sub 2}(OAc){sub 4} gave purple {l_brace}(Et{sub 4}N){sub 2}[Cp*Ir(CN){sub 3}]{sub 2}[Rh{sub 2}(O{sub 2}CCF{sub 3}){sub 4}]{sub 3}{r_brace}, whose insolubility is attributed to stronger Rh-NC bonds as well as the presence of cross-linking. The species {l_brace}[Cp*Rh(CN){sub 3}][Ni(en){sub n}](PF{sub 6}){r_brace} (n = 2, 3) crystallized from an aqueous solution of Et{sub 4}N[Cp*Rh(CN){sub 3}] and [Ni(en){sub 3}](PF{sub 6}){sub 2}; {l_brace}[Cp*Rh(CN){sub 3}][Ni(en){sub 2}](PF{sub 6}){r_brace} consists of helical chains based on cis-Ni(en){sub 2}{sup 2+} units. Aqueous solutions of Et{sub 4}N[Cp*Ir(CN){sub 3}] and AgNO{sub 3} afforded the colorless solid Ag[Cp*Ir(CN){sub 3}]. Recrystallization of this polymer from pyridine gave the hemipyridine adduct {l_brace}Ag[Ag(py)][Cp*Ir(CN){sub 3}]{sub 2}{r_brace}. The {sup 13}C cross-polarization magic-angle spinning NMR spectrum of the pyridine derivative reveals two distinct Cp* groups, while in the pyridine-free precursor, the Cp*'s appear equivalent. The solid-state structure of {l_brace}Ag[Ag(py)][Cp*Ir(CN){sub 3}]{sub 2}{r_brace} reveals a three-dimensional coordination polymer consisting of chains of Cp*Ir(CN){sub 3}{sup {minus}} units linked to alternating Ag{sup +} and Ag(py){sup +} units. The network structure arises by the linking of these helices through the third cyanide group on each Ir center.

• Research Organization: Univ. of Illinois, Urbana, IL (US)
• Sponsoring Organization: US Department of Energy
• OSTI ID: 20075874
• Journal Information: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 10 Vol. 39; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
CRYSTAL STRUCTURE
CYANIDES
IRIDIUM COMPLEXES
NUCLEAR MAGNETIC RESONANCE
PYRIDINES
RHODIUM COMPLEXES
SOLIDS
SYNTHESIS