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

Title: Synthesis and coordination chemistry of the first water-soluble dithio-bis(phosphine) ligands [(HOH{sub 2}C){sub 2}P(CH{sub 2}){sub 2}S-X-S(CH{sub 2}){sub 2}P(CH{sub 2}OH){sub 2}] (X = (CH{sub 2}){sub 3} or C{sub 6}H{sub 4}). X-ray crystal structure of [Pd(HOH{sub 2}C){sub 2}P(CH{sub 2}){sub 2}S(CH{sub 2}){sub 3}S(CH{sub 2}){sub 2}P(CH{sub 2}OH){sub 2}](Cl){sub 2}

Abstract

The thioether-functionalized, water-soluble, bis(phosphines) (HOH{sub 2}C){sub 2}PCH{sub 2}CH{sub 2}S(CH{sub 2}){sub 3}SCH{sub 2}CH{sub 2}P(CH{sub 2}OH){sub 2} (9) and C{sub 6}H{sub 4}(1,2-SCH{sub 2}CH{sub 2}P(CH{sub 2}OH){sub 2}){sub 2}(10) were synthesized in near quantitative yields by the formylation of the appropriate phosphine hydrides in the presence of formaldehyde in ethanol. The reactions of 9 and 10 with Pt(COD)Cl{sub 2} an Pd(C{sub 6}H{sub 5}CN){sub 2}Cl{sub 2} in biphasic media (aqueous/organic) produced the water-soluble Pt(II) and Pd(II) complexes [Pt(HOH{sub 2}C){sub 2}P(CH{sub 2}){sub 2}S(CH{sub 2}){sub 3}S(CH{sub 2}){sub 2}P(CH{sub 2}OH){sub 2}](Cl){sub 2} (11), [Pd(HOH{sub 2}C){sub 2}P(CH{sub 2}){sub 2}S(CH{sub 2}){sub 3}S(CH{sub 2}){sub 2{minus}}P(CH{sub 2}OH){sub 2}](Cl){sub 2} (12), [Pt((C{sub 6}H{sub 4})(1,2-S(CH{sub 2}){sub 2}P(CH{sub 2}OH){sub 2}){sub 2})](Cl){sub 2} (13), and [Pd((C{sub 6}H{sub 4})(1,2-S(CH{sub 2}){sub 2}P(CH{sub 2}OH){sub 2}){sub 2})](Cl){sub 2} (14) in near quantitative yields. The X-ray crystal structure of 12 confirms a square-planar Pd(II) structure for this new generation of water-soluble transition metal complexes. All of the complexes were characterized by MS, H, C, and P NMR spectroscopy. X-ray data for 12: triclinic, P1, a = 9.9761(6) {angstrom}, b = 10.2049(7) {angstrom}, c = 11.6954(7) {angstrom}, a = 67.730(10){degrees}, {beta} = 69.943(10){degrees}, {gamma} = 79.828(10){degrees}, Z = 2, R = 0.0307 (R{sub w} = 0.0797).

Authors:
; ;  [1]
  1. Univ. of Missouri, Columbia, MO (United States) [and others
Publication Date:
OSTI Identifier:
518417
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 36; Journal Issue: 9; Other Information: PBD: 23 Apr 1997
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; ORGANIC SULFUR COMPOUNDS; CHEMICAL PREPARATION; STRUCTURAL CHEMICAL ANALYSIS; ORGANIC PHOSPHORUS COMPOUNDS; PLATINUM COMPLEXES; PALLADIUM COMPLEXES; LIGANDS; CRYSTAL STRUCTURE; NUCLEAR MAGNETIC RESONANCE; TRICLINIC LATTICES; CHEMICAL REACTION YIELD; X-RAY DIFFRACTION

Citation Formats

Smith, C.J., Reddy, V.S., and Karra, S.R. Synthesis and coordination chemistry of the first water-soluble dithio-bis(phosphine) ligands [(HOH{sub 2}C){sub 2}P(CH{sub 2}){sub 2}S-X-S(CH{sub 2}){sub 2}P(CH{sub 2}OH){sub 2}] (X = (CH{sub 2}){sub 3} or C{sub 6}H{sub 4}). X-ray crystal structure of [Pd(HOH{sub 2}C){sub 2}P(CH{sub 2}){sub 2}S(CH{sub 2}){sub 3}S(CH{sub 2}){sub 2}P(CH{sub 2}OH){sub 2}](Cl){sub 2}. United States: N. p., 1997. Web. doi:10.1021/ic961319g.
Smith, C.J., Reddy, V.S., & Karra, S.R. Synthesis and coordination chemistry of the first water-soluble dithio-bis(phosphine) ligands [(HOH{sub 2}C){sub 2}P(CH{sub 2}){sub 2}S-X-S(CH{sub 2}){sub 2}P(CH{sub 2}OH){sub 2}] (X = (CH{sub 2}){sub 3} or C{sub 6}H{sub 4}). X-ray crystal structure of [Pd(HOH{sub 2}C){sub 2}P(CH{sub 2}){sub 2}S(CH{sub 2}){sub 3}S(CH{sub 2}){sub 2}P(CH{sub 2}OH){sub 2}](Cl){sub 2}. United States. doi:10.1021/ic961319g.
Smith, C.J., Reddy, V.S., and Karra, S.R. Wed . "Synthesis and coordination chemistry of the first water-soluble dithio-bis(phosphine) ligands [(HOH{sub 2}C){sub 2}P(CH{sub 2}){sub 2}S-X-S(CH{sub 2}){sub 2}P(CH{sub 2}OH){sub 2}] (X = (CH{sub 2}){sub 3} or C{sub 6}H{sub 4}). X-ray crystal structure of [Pd(HOH{sub 2}C){sub 2}P(CH{sub 2}){sub 2}S(CH{sub 2}){sub 3}S(CH{sub 2}){sub 2}P(CH{sub 2}OH){sub 2}](Cl){sub 2}". United States. doi:10.1021/ic961319g.
@article{osti_518417,
title = {Synthesis and coordination chemistry of the first water-soluble dithio-bis(phosphine) ligands [(HOH{sub 2}C){sub 2}P(CH{sub 2}){sub 2}S-X-S(CH{sub 2}){sub 2}P(CH{sub 2}OH){sub 2}] (X = (CH{sub 2}){sub 3} or C{sub 6}H{sub 4}). X-ray crystal structure of [Pd(HOH{sub 2}C){sub 2}P(CH{sub 2}){sub 2}S(CH{sub 2}){sub 3}S(CH{sub 2}){sub 2}P(CH{sub 2}OH){sub 2}](Cl){sub 2}},
author = {Smith, C.J. and Reddy, V.S. and Karra, S.R.},
abstractNote = {The thioether-functionalized, water-soluble, bis(phosphines) (HOH{sub 2}C){sub 2}PCH{sub 2}CH{sub 2}S(CH{sub 2}){sub 3}SCH{sub 2}CH{sub 2}P(CH{sub 2}OH){sub 2} (9) and C{sub 6}H{sub 4}(1,2-SCH{sub 2}CH{sub 2}P(CH{sub 2}OH){sub 2}){sub 2}(10) were synthesized in near quantitative yields by the formylation of the appropriate phosphine hydrides in the presence of formaldehyde in ethanol. The reactions of 9 and 10 with Pt(COD)Cl{sub 2} an Pd(C{sub 6}H{sub 5}CN){sub 2}Cl{sub 2} in biphasic media (aqueous/organic) produced the water-soluble Pt(II) and Pd(II) complexes [Pt(HOH{sub 2}C){sub 2}P(CH{sub 2}){sub 2}S(CH{sub 2}){sub 3}S(CH{sub 2}){sub 2}P(CH{sub 2}OH){sub 2}](Cl){sub 2} (11), [Pd(HOH{sub 2}C){sub 2}P(CH{sub 2}){sub 2}S(CH{sub 2}){sub 3}S(CH{sub 2}){sub 2{minus}}P(CH{sub 2}OH){sub 2}](Cl){sub 2} (12), [Pt((C{sub 6}H{sub 4})(1,2-S(CH{sub 2}){sub 2}P(CH{sub 2}OH){sub 2}){sub 2})](Cl){sub 2} (13), and [Pd((C{sub 6}H{sub 4})(1,2-S(CH{sub 2}){sub 2}P(CH{sub 2}OH){sub 2}){sub 2})](Cl){sub 2} (14) in near quantitative yields. The X-ray crystal structure of 12 confirms a square-planar Pd(II) structure for this new generation of water-soluble transition metal complexes. All of the complexes were characterized by MS, H, C, and P NMR spectroscopy. X-ray data for 12: triclinic, P1, a = 9.9761(6) {angstrom}, b = 10.2049(7) {angstrom}, c = 11.6954(7) {angstrom}, a = 67.730(10){degrees}, {beta} = 69.943(10){degrees}, {gamma} = 79.828(10){degrees}, Z = 2, R = 0.0307 (R{sub w} = 0.0797).},
doi = {10.1021/ic961319g},
journal = {Inorganic Chemistry},
number = 9,
volume = 36,
place = {United States},
year = {1997},
month = {4}
}