Synthesis and reactivity of copper(I) phosphine-alkene complexes: X-ray crystal structure of CuCl(Ph2PCPh=CH2)(2)
Synthesis and reactivity of copper(I) phosphine-alkene complexes: X-ray crystal structure of CuCl(Ph2PCPh=CH2)(2)
Copper(I) chloride complexes containing bifunctional phosphine/alkene ligands of the form CuCl(Ph2PCH=CH2)(n) (n = 1, 3) and CuCl( Ph2PCPh=CH2)(2) have been synthesized, with the latter being characterized by single crystal X-ray diffraction. Complexes decompose rapidly on reaction with hydroborating agents NaBH4 and Na[B(OMe)(3)H], although the thermally unstable Cu(BH4) (Ph2PCPh=CH2)(2) may be observed by NMR spectroscopy. The complexes show considerable resistance to thermally initiated alkene polymerization, the only significant reactivity for diphenylvinylphosphine complexes being trace ligand dissociation and subsequent aerobic oxidation to Ph2P(O)CH=CH2. Similar dissociation/oxidation is not observed for CuCl(Ph2PCPh=CH2)(2). Lewis acid initiated polymerization, using Et2O . BF3, results in the facile formation of copper(I) coordinated polymeric phosphine ligands for diphenylvinylphosphine complexes, but again no reactivity is induced in the more sterically hindered alpha-styrenyl analogue.
phosphine, alkene, polymerization, hydroboration, copper(i) complexes
group-11 metal(i) compounds, lewis-base adducts, solid-state, p-31 nmr, chloride, ligands, triphenylphosphine, mononuclear, halides
1271-1278
Goles, S. J.
65c3706b-69a3-4df0-b48d-83080fb36dfe
Faulds, P.
d9dd0325-d900-446c-a428-4eb57d6947f3
Hursthouse, M. B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Kelly, D. G.
c64371f1-a702-439f-9c18-50a5b25ba64c
Toner, A. J.
3a1b0c3b-73bc-400b-a681-babb3838e2f6
30 May 2000
Goles, S. J.
65c3706b-69a3-4df0-b48d-83080fb36dfe
Faulds, P.
d9dd0325-d900-446c-a428-4eb57d6947f3
Hursthouse, M. B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Kelly, D. G.
c64371f1-a702-439f-9c18-50a5b25ba64c
Toner, A. J.
3a1b0c3b-73bc-400b-a681-babb3838e2f6
Goles, S. J., Faulds, P., Hursthouse, M. B., Kelly, D. G. and Toner, A. J.
(2000)
Synthesis and reactivity of copper(I) phosphine-alkene complexes: X-ray crystal structure of CuCl(Ph2PCPh=CH2)(2).
Polyhedron, 19 (10), .
(doi:10.1016/S0277-5387(00)00386-7).
Abstract
Copper(I) chloride complexes containing bifunctional phosphine/alkene ligands of the form CuCl(Ph2PCH=CH2)(n) (n = 1, 3) and CuCl( Ph2PCPh=CH2)(2) have been synthesized, with the latter being characterized by single crystal X-ray diffraction. Complexes decompose rapidly on reaction with hydroborating agents NaBH4 and Na[B(OMe)(3)H], although the thermally unstable Cu(BH4) (Ph2PCPh=CH2)(2) may be observed by NMR spectroscopy. The complexes show considerable resistance to thermally initiated alkene polymerization, the only significant reactivity for diphenylvinylphosphine complexes being trace ligand dissociation and subsequent aerobic oxidation to Ph2P(O)CH=CH2. Similar dissociation/oxidation is not observed for CuCl(Ph2PCPh=CH2)(2). Lewis acid initiated polymerization, using Et2O . BF3, results in the facile formation of copper(I) coordinated polymeric phosphine ligands for diphenylvinylphosphine complexes, but again no reactivity is induced in the more sterically hindered alpha-styrenyl analogue.
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Published date: 30 May 2000
Keywords:
phosphine, alkene, polymerization, hydroboration, copper(i) complexes
group-11 metal(i) compounds, lewis-base adducts, solid-state, p-31 nmr, chloride, ligands, triphenylphosphine, mononuclear, halides
Identifiers
Local EPrints ID: 18879
URI: http://eprints.soton.ac.uk/id/eprint/18879
ISSN: 0277-5387
PURE UUID: a130078a-c39e-4826-aca8-3aa7af85b91c
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Date deposited: 16 Dec 2005
Last modified: 15 Mar 2024 06:08
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Contributors
Author:
S. J. Goles
Author:
P. Faulds
Author:
D. G. Kelly
Author:
A. J. Toner
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