Reactions of isocyanides with rhodium porphyrins. Formation of formimidoyl and carbamoyl complexes and CN-R bond cleavage

Poszmik, G; Carroll, P J; Wayland, B B

doi:10.1021/om00033a010

Title: Reactions of isocyanides with rhodium porphyrins. Formation of formimidoyl and carbamoyl complexes and CN-R bond cleavage

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Abstract

Reactions of alkyl and aryl isocyanides with (octaethylporphyrinato)rhodium hydride, (OEP)Rh-H, (octaethylporphyrinato)rhodium(II) dimer, [(OEP)Rh][sub 2] and (tetramesitylporphyrinato)rhodium(II), (TMP)Rh, have been investigated for comparison with CO reactivity. Alkyl and aryl isocyanides interact with (OEP)Rh-H to form 1:1 adducts, (OEP)Rh(H)(CNR), which react further to produce formimidoyl complexes, (OEP)Rh-CH=NR, in analog with the reaction of (OEP)Rh-H with CO that produces a formyl complex, (OEP)Rh-CHO. [(OEP)Rh][sub 2] forms 1:1 complexes with isocyanides where the 2,6-dimethylphenyl isocyanide derivative persists at equilibrium, but alkyl isocyanides undergo CN- alkyl bond cleavage to form alkyl, (OEP)Rh-R and cyanide, (OEP)Rh(CN)(CNR), complexes. No evidence was obtained for bridging isocyanide species analogous to the dimetal ketone RhC(O)Rh and dimetal diketone RhC(O)C(O)Rh complexes observed in reactions of [(OEP)Rh][sub 2] with CO. Carbamoyl complexes, (OEP)Rh-C(O)NHR, are formed in reactions of [(OEP)Rh][sub 2] with CNR and H[sub 2]O or CO and RNH[sub 2]. 24 refs., 7 figs., 3 tabs.

Authors:

Poszmik, G; Carroll, P J; Wayland, B B ^[1]

Univ. of Pennsylvania, Philadelphia, PA (United States)

Publication Date:: Wed Sep 01 00:00:00 EDT 1993

OSTI Identifier:: 5651916

DOE Contract Number:: FG02-86ER13615

Resource Type:: Journal Article

Journal Name:: Organometallics; (United States)

Additional Journal Information:: Journal Volume: 12:9; Journal ID: ISSN 0276-7333

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CARBON MONOXIDE; CHEMICAL REACTIONS; PORPHYRINS; RHODIUM COMPLEXES; CRYSTAL STRUCTURE; ELECTRON SPIN RESONANCE; EXPERIMENTAL DATA; MOLECULAR STRUCTURE; NMR SPECTRA; ORGANOMETALLIC COMPOUNDS; CARBON COMPOUNDS; CARBON OXIDES; CARBOXYLIC ACIDS; CHALCOGENIDES; COMPLEXES; DATA; HETEROCYCLIC ACIDS; HETEROCYCLIC COMPOUNDS; INFORMATION; MAGNETIC RESONANCE; NUMERICAL DATA; ORGANIC ACIDS; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; OXIDES; OXYGEN COMPOUNDS; RESONANCE; SPECTRA; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties; 400102 - Chemical & Spectral Procedures

Citation Formats


                    Poszmik, G, Carroll, P J, and Wayland, B B. Reactions of isocyanides with rhodium porphyrins. Formation of formimidoyl and carbamoyl complexes and CN-R bond cleavage.  United States: N. p., 1993. 
        Web.  doi:10.1021/om00033a010.

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                    Poszmik, G, Carroll, P J, & Wayland, B B. Reactions of isocyanides with rhodium porphyrins. Formation of formimidoyl and carbamoyl complexes and CN-R bond cleavage.  United States.  https://doi.org/10.1021/om00033a010

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                    Poszmik, G, Carroll, P J, and Wayland, B B. 1993.  
        "Reactions of isocyanides with rhodium porphyrins. Formation of formimidoyl and carbamoyl complexes and CN-R bond cleavage".  United States.  https://doi.org/10.1021/om00033a010.

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@article{osti_5651916,

  title        = {Reactions of isocyanides with rhodium porphyrins. Formation of formimidoyl and carbamoyl complexes and CN-R bond cleavage},

  author       = {Poszmik, G and Carroll, P J and Wayland, B B},

  abstractNote = {Reactions of alkyl and aryl isocyanides with (octaethylporphyrinato)rhodium hydride, (OEP)Rh-H, (octaethylporphyrinato)rhodium(II) dimer, [(OEP)Rh][sub 2] and (tetramesitylporphyrinato)rhodium(II), (TMP)Rh, have been investigated for comparison with CO reactivity. Alkyl and aryl isocyanides interact with (OEP)Rh-H to form 1:1 adducts, (OEP)Rh(H)(CNR), which react further to produce formimidoyl complexes, (OEP)Rh-CH=NR, in analog with the reaction of (OEP)Rh-H with CO that produces a formyl complex, (OEP)Rh-CHO. [(OEP)Rh][sub 2] forms 1:1 complexes with isocyanides where the 2,6-dimethylphenyl isocyanide derivative persists at equilibrium, but alkyl isocyanides undergo CN- alkyl bond cleavage to form alkyl, (OEP)Rh-R and cyanide, (OEP)Rh(CN)(CNR), complexes. No evidence was obtained for bridging isocyanide species analogous to the dimetal ketone RhC(O)Rh and dimetal diketone RhC(O)C(O)Rh complexes observed in reactions of [(OEP)Rh][sub 2] with CO. Carbamoyl complexes, (OEP)Rh-C(O)NHR, are formed in reactions of [(OEP)Rh][sub 2] with CNR and H[sub 2]O or CO and RNH[sub 2]. 24 refs., 7 figs., 3 tabs.},

  doi          = {10.1021/om00033a010},

  url          = {https://www.osti.gov/biblio/5651916},
  journal      = {Organometallics; (United States)},

  issn         = {0276-7333},

  number       = ,

  volume       = 12:9,

  place        = {United States},

  year         = {Wed Sep 01 00:00:00 EDT 1993},

  month        = {Wed Sep 01 00:00:00 EDT 1993}

}

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