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Title: Syntheses and structures of alkyl and aryl halide complexes of the type [(PiPr{sub 3}){sub 2}PtH({eta}{sup 1}-XR)]BAr{sub f} and analogues with Et{sub 2}O, THF, and H{sub 2} ligands. Halide-to-metal {pi}-bonding in halocarbon complexes

Abstract

The reaction of Pt(PiPr{sub 3}){sub 3} with SO{sub 2} led to the formation of (PiPr{sub 3}){sub 2}Pt(SO{sub 2}) (1), isolated in 93% yield. The addition of [H(OEt{sub 2}){sub 2}]{sup +}BAr{sub f} (BAr{sub f} = B(3,5-(CF{sub 3}){sub 2}C{sub 6}H{sub 3}){sub 4}) to 1 in ether at -78 {degree}C afforded the solved complex trans-[(PiPr{sub 3}){sub 2}Pt(H)(OEt{sub 2})]BAr{sub f}(2) in 85% isolated yield. Complex 2 served as a precursor to monodentate halocarbon complexes of the type Pt({eta}{sup 1}-XR). The dichloromethane complex trans-[(PiPr{sub 3}){sub 2}Pt(H)({eta}{sup 1} -ClCH{sub 2}Cl)]BAr{sub f} (3) was isolated in 80% yield by the recrystallization of 2 from CH{sub 2}Cl{sub 2}/hexane. TR spectroscopy suggested the existence of dichloromethane binding which was confirmed by X-ray crystallography. The reaction of 2 or 3 with iodo- or bromobenzene led to the isolation of the haloarene complexes trans-[(PiPr{sub 3}){sub 2}Pt(H)({eta}{sup 1}-XPh)]BAr{sub f}, where X = I (4, 87% yield) or Br (5, 60% yield). An unexpected steric interaction in 4, suggested by molecular mechanics calculations to be significant, was rationalized in terms of halide-to-metal {pi} bonding. The PhI complex 4 decomposed under harsh conditions to the bridging iodide compound [trans-[(PiPr{sub 3}){sub 2}Pt(H)]{sub 2}({mu}-I)] Ar{sub f} (6) which was structurally characterized. The THF adduct [(PiPr{sub 3}){submore » 2}-Pt(H)(THF)]Ar{sub f} (7) was formed when any of the compounds 2,3,4, or 5 was dissolved in THF. 58 refs., 8 figs., 5 tabs.« less

Authors:
; ;  [1]
  1. Los Alamos National Lab., NM (United States)
Publication Date:
OSTI Identifier:
437400
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 118; Journal Issue: 47; Other Information: PBD: 27 Nov 1996
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; PLATINUM COMPLEXES; SYNTHESIS; STRUCTURAL CHEMICAL ANALYSIS; NMR SPECTRA; ORGANOMETALLIC COMPOUNDS; ADDUCTS; X-RAY DIFFRACTION; CRYSTALLOGRAPHY; CHEMICAL BONDS; BOND LENGTHS; BOND ANGLE; MOLECULAR ORBITAL METHOD; ORGANIC CHLORINE COMPOUNDS; ORGANIC IODINE COMPOUNDS; ORGANIC BROMINE COMPOUNDS

Citation Formats

Butts, M D, Scott, B L, and Kubas, G J. Syntheses and structures of alkyl and aryl halide complexes of the type [(PiPr{sub 3}){sub 2}PtH({eta}{sup 1}-XR)]BAr{sub f} and analogues with Et{sub 2}O, THF, and H{sub 2} ligands. Halide-to-metal {pi}-bonding in halocarbon complexes. United States: N. p., 1996. Web. doi:10.1021/ja961836y.
Butts, M D, Scott, B L, & Kubas, G J. Syntheses and structures of alkyl and aryl halide complexes of the type [(PiPr{sub 3}){sub 2}PtH({eta}{sup 1}-XR)]BAr{sub f} and analogues with Et{sub 2}O, THF, and H{sub 2} ligands. Halide-to-metal {pi}-bonding in halocarbon complexes. United States. doi:10.1021/ja961836y.
Butts, M D, Scott, B L, and Kubas, G J. Wed . "Syntheses and structures of alkyl and aryl halide complexes of the type [(PiPr{sub 3}){sub 2}PtH({eta}{sup 1}-XR)]BAr{sub f} and analogues with Et{sub 2}O, THF, and H{sub 2} ligands. Halide-to-metal {pi}-bonding in halocarbon complexes". United States. doi:10.1021/ja961836y.
@article{osti_437400,
title = {Syntheses and structures of alkyl and aryl halide complexes of the type [(PiPr{sub 3}){sub 2}PtH({eta}{sup 1}-XR)]BAr{sub f} and analogues with Et{sub 2}O, THF, and H{sub 2} ligands. Halide-to-metal {pi}-bonding in halocarbon complexes},
author = {Butts, M D and Scott, B L and Kubas, G J},
abstractNote = {The reaction of Pt(PiPr{sub 3}){sub 3} with SO{sub 2} led to the formation of (PiPr{sub 3}){sub 2}Pt(SO{sub 2}) (1), isolated in 93% yield. The addition of [H(OEt{sub 2}){sub 2}]{sup +}BAr{sub f} (BAr{sub f} = B(3,5-(CF{sub 3}){sub 2}C{sub 6}H{sub 3}){sub 4}) to 1 in ether at -78 {degree}C afforded the solved complex trans-[(PiPr{sub 3}){sub 2}Pt(H)(OEt{sub 2})]BAr{sub f}(2) in 85% isolated yield. Complex 2 served as a precursor to monodentate halocarbon complexes of the type Pt({eta}{sup 1}-XR). The dichloromethane complex trans-[(PiPr{sub 3}){sub 2}Pt(H)({eta}{sup 1} -ClCH{sub 2}Cl)]BAr{sub f} (3) was isolated in 80% yield by the recrystallization of 2 from CH{sub 2}Cl{sub 2}/hexane. TR spectroscopy suggested the existence of dichloromethane binding which was confirmed by X-ray crystallography. The reaction of 2 or 3 with iodo- or bromobenzene led to the isolation of the haloarene complexes trans-[(PiPr{sub 3}){sub 2}Pt(H)({eta}{sup 1}-XPh)]BAr{sub f}, where X = I (4, 87% yield) or Br (5, 60% yield). An unexpected steric interaction in 4, suggested by molecular mechanics calculations to be significant, was rationalized in terms of halide-to-metal {pi} bonding. The PhI complex 4 decomposed under harsh conditions to the bridging iodide compound [trans-[(PiPr{sub 3}){sub 2}Pt(H)]{sub 2}({mu}-I)] Ar{sub f} (6) which was structurally characterized. The THF adduct [(PiPr{sub 3}){sub 2}-Pt(H)(THF)]Ar{sub f} (7) was formed when any of the compounds 2,3,4, or 5 was dissolved in THF. 58 refs., 8 figs., 5 tabs.},
doi = {10.1021/ja961836y},
journal = {Journal of the American Chemical Society},
number = 47,
volume = 118,
place = {United States},
year = {1996},
month = {11}
}