skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Alkyl and hydrido phenoxo complexes of nickel(II), palladium(II), and platinum(II). Hydrido amido complexes of palladium

Abstract

The compound trans-NiHCl(PBz{sub 3}){sub 2}, where Bz=CH{sub 2}C{sub 6}H{sub 5}, has been synthesized in good yield by the reduction of NiCl{sub 2}(PBz{sub 3}){sub 2} with Super-Hydride, whereas the Pd and Pt analogues may be prepared by reduction of the corresponding MCl{sub 2}(PBz{sub 3}){sub 2} complexes with sodium naphthalide under an ethylene atmosphere, followed by the addition of HCl. Addition of NaOPh to trans-NiHCl(P{sup 1}Pr{sub 3}){sub 2} or trans-NiHCl(PCy{sub 3}){sub 2}, where {sup i}Pr = i-C{sub 3}H{sub 7} and Cy = c-C{sub 6}H{sub 11}, produces the corresponding hydrido phenoxo complexes, while the addition of NaOPh to trans-NiHCl(PBz{sub 3}){sub 2} yields trans-NiH(OPh)(PBz{sub 3}){sub 2}{center dot}HOPh. Addition of phenol to Pd(CH{sub 3}){sub 2}(dmpe), where dmpe = 1,2-bis(dimethyl-phosphino)ethane, yields Pd(CH{sub 3})(OPh)(dmpe). The reactivity of these late-transition-metal phenoxides suggests a high nucleophilicity for the metal-bound phenoxide, as evidenced by alkylation at oxygen by methyl iodide or by the insertion of an electrophile such as phenyl isocyanate. Thermally unstable hydrido anilido complexes trans-PdH(NHPh)L{sub 2}, where L = P({sup i}Pr){sub 3} or PCy{sub 3}, were prepared by addition of NaNHPh to the corresponding hydrido chloro complexes. With the use of Na{sup 15}NHPh it was possible to definitively characterize the solution structures of these unstable species by NMRmore » spectroscopy. Besides exhibiting alkylation and insertion reactivity similar to the phenoxide complexes, these compounds were extremely susceptible to reductive elimination of aniline on addition of ligands, such as acrylonitrile. A consideration of bond strengths, along with the observed tendencies for reductive elimination, suggests that catalytic animation of olefins by a cycle that requires N-H oxidative addition has thermodynamic limitations for the late transition metals.« less

Authors:
; ;  [1]
  1. Univ. of California, San Diego, La Jolla (United States)
Publication Date:
OSTI Identifier:
7163708
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry; (United States)
Additional Journal Information:
Journal Volume: 30:18; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ORGANOMETALLIC COMPOUNDS; CHEMICAL PREPARATION; PALLADIUM COMPLEXES; ACRYLONITRILE; ALKYLATION; ATMOSPHERES; BOND LENGTHS; CRYSTAL STRUCTURE; ETHYLENE; HYDROCHLORIC ACID; LIGANDS; METHYL IODIDE; NICKEL COMPLEXES; NMR SPECTRA; ORTHORHOMBIC LATTICES; PHENOL; PLATINUM COMPLEXES; REDUCTION; TRICLINIC LATTICES; ALKENES; AROMATICS; CHEMICAL REACTIONS; CHLORINE COMPOUNDS; COMPLEXES; CRYSTAL LATTICES; DIMENSIONS; HALOGEN COMPOUNDS; HALOGENATED ALIPHATIC HYDROCARBONS; HYDROCARBONS; HYDROGEN COMPOUNDS; HYDROXY COMPOUNDS; INORGANIC ACIDS; IODINATED ALIPHATIC HYDROCARBONS; LENGTH; NITRILES; ORGANIC COMPOUNDS; ORGANIC HALOGEN COMPOUNDS; ORGANIC IODINE COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; PHENOLS; SPECTRA; SYNTHESIS; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties

Citation Formats

Seligson, A L, Cowan, R L, and Trogler, W C. Alkyl and hydrido phenoxo complexes of nickel(II), palladium(II), and platinum(II). Hydrido amido complexes of palladium. United States: N. p., 1991. Web. doi:10.1021/ic00018a003.
Seligson, A L, Cowan, R L, & Trogler, W C. Alkyl and hydrido phenoxo complexes of nickel(II), palladium(II), and platinum(II). Hydrido amido complexes of palladium. United States. https://doi.org/10.1021/ic00018a003
Seligson, A L, Cowan, R L, and Trogler, W C. 1991. "Alkyl and hydrido phenoxo complexes of nickel(II), palladium(II), and platinum(II). Hydrido amido complexes of palladium". United States. https://doi.org/10.1021/ic00018a003.
@article{osti_7163708,
title = {Alkyl and hydrido phenoxo complexes of nickel(II), palladium(II), and platinum(II). Hydrido amido complexes of palladium},
author = {Seligson, A L and Cowan, R L and Trogler, W C},
abstractNote = {The compound trans-NiHCl(PBz{sub 3}){sub 2}, where Bz=CH{sub 2}C{sub 6}H{sub 5}, has been synthesized in good yield by the reduction of NiCl{sub 2}(PBz{sub 3}){sub 2} with Super-Hydride, whereas the Pd and Pt analogues may be prepared by reduction of the corresponding MCl{sub 2}(PBz{sub 3}){sub 2} complexes with sodium naphthalide under an ethylene atmosphere, followed by the addition of HCl. Addition of NaOPh to trans-NiHCl(P{sup 1}Pr{sub 3}){sub 2} or trans-NiHCl(PCy{sub 3}){sub 2}, where {sup i}Pr = i-C{sub 3}H{sub 7} and Cy = c-C{sub 6}H{sub 11}, produces the corresponding hydrido phenoxo complexes, while the addition of NaOPh to trans-NiHCl(PBz{sub 3}){sub 2} yields trans-NiH(OPh)(PBz{sub 3}){sub 2}{center dot}HOPh. Addition of phenol to Pd(CH{sub 3}){sub 2}(dmpe), where dmpe = 1,2-bis(dimethyl-phosphino)ethane, yields Pd(CH{sub 3})(OPh)(dmpe). The reactivity of these late-transition-metal phenoxides suggests a high nucleophilicity for the metal-bound phenoxide, as evidenced by alkylation at oxygen by methyl iodide or by the insertion of an electrophile such as phenyl isocyanate. Thermally unstable hydrido anilido complexes trans-PdH(NHPh)L{sub 2}, where L = P({sup i}Pr){sub 3} or PCy{sub 3}, were prepared by addition of NaNHPh to the corresponding hydrido chloro complexes. With the use of Na{sup 15}NHPh it was possible to definitively characterize the solution structures of these unstable species by NMR spectroscopy. Besides exhibiting alkylation and insertion reactivity similar to the phenoxide complexes, these compounds were extremely susceptible to reductive elimination of aniline on addition of ligands, such as acrylonitrile. A consideration of bond strengths, along with the observed tendencies for reductive elimination, suggests that catalytic animation of olefins by a cycle that requires N-H oxidative addition has thermodynamic limitations for the late transition metals.},
doi = {10.1021/ic00018a003},
url = {https://www.osti.gov/biblio/7163708}, journal = {Inorganic Chemistry; (United States)},
issn = {0020-1669},
number = ,
volume = 30:18,
place = {United States},
year = {1991},
month = {9}
}