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

Abstract

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 ofmore » {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.« less

Authors:
; ;
Publication Date:
Research Org.:
Univ. of Illinois, Urbana, IL (US)
Sponsoring Org.:
USDOE
OSTI Identifier:
20075874
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 39; Journal Issue: 10; Other Information: PBD: 15 May 2000; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; RHODIUM COMPLEXES; IRIDIUM COMPLEXES; CYANIDES; CRYSTAL STRUCTURE; PYRIDINES; SYNTHESIS; SOLIDS; NUCLEAR MAGNETIC RESONANCE

Citation Formats

Contakes, S.M., Klausmeyer, K.K., and Rauchfuss, T.B. Coordination solids derived from Cp*M(CN){sub 3}{sup {minus}} (M = Rh, Ir). United States: N. p., 2000. Web. doi:10.1021/ic991037r.
Contakes, S.M., Klausmeyer, K.K., & Rauchfuss, T.B. Coordination solids derived from Cp*M(CN){sub 3}{sup {minus}} (M = Rh, Ir). United States. doi:10.1021/ic991037r.
Contakes, S.M., Klausmeyer, K.K., and Rauchfuss, T.B. Mon . "Coordination solids derived from Cp*M(CN){sub 3}{sup {minus}} (M = Rh, Ir)". United States. doi:10.1021/ic991037r.
@article{osti_20075874,
title = {Coordination solids derived from Cp*M(CN){sub 3}{sup {minus}} (M = Rh, Ir)},
author = {Contakes, S.M. and Klausmeyer, K.K. and Rauchfuss, T.B.},
abstractNote = {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.},
doi = {10.1021/ic991037r},
journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 10,
volume = 39,
place = {United States},
year = {2000},
month = {5}
}