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SYNTHESIS OF CIS-CR)2(PPh3)2> AND TRANS-CR)(PPh3)2> COMPLEXES. CRYSTAL AND MOLECULAR STRUCTURES OF CIS-CC(OH)Me2>2(PPh3)2>*H2O, TRANS-CC(OH)Me2>(PPh3)2>*0.5PhMe, AND TRANS-CC(OH)MeEt>(PPh3)2>*Me2CO. INFLUENCE OF BASES AND THEIR CONCENTRATI...

DOI: 10.1039/DT9840002197

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2197 - 2206 (1984)

Update date:2022-08-04

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Authors:

Furlani, AnitaFurlani, Anita

Licoccia, SilviaLicoccia, Silvia

Russo, Maria V.Russo, Maria V.

Villa, Angiola ChiesiVilla, Angiola Chiesi

Guastini, CarloGuastini, Carlo

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Article abstract of DOI:10.1039/DT9840002197

Complexes cis-CR)2(PPh3)2> can be obtained from cis- and HC<*>CR in 30 percent aqueous ammonia as solvent.Complexes trans-CR)(PPh3)2> are obtained by using chloroform (or dichloromethane)-diethylamine as solvent.No dehydration reactions of the acetylenic alcohols are observed.X-ray analyses on cis-CC(OH)Me2>2(PPh3)2>*H2O, trans-CC(OH)Me2>(PPh3)2>*0.5PhMe, and trans-CC(OH)MeEt>(PPh3)2>*Me2CO revealed in the cis complex the presence of a water molecule forming two strong hydrogen bond with the two cis-oriented hydroxy-groups of the acetylide ligands.In all the complexes the co-ordination around platinum is distorted square planar with the acetylide ligands ?-bonded to platinum.Crystallographic details: cis-CC(OH)Me2>2(PPh3)2>*H2O, monoclinic, space group P21/c, with a = 15.473(5), b = 21.725(6), c = 13.439(4) Angstroem, β = 113.95(3)deg, and Z = 4; R 0.052 for 3 110 observed reflections; trans-CC(OH)Me2>(PPh3)2>*0.5PhMe, triclinic, space group P<*>, with a = 11.695(3), b = 19.690(6), c = 9.214(2) Angstroem, α = 101.88(3), β = 104.26(3), γ = 85.55(3)deg, and Z = 2; R = 0.053 for 3 961 observed reflections; CC(OH)MeEt>(PPh3)2>*Me2CO, triclinic, space group P<*>, with a = 15.544(6), b = 12.567(4), c = 11.719(3) Angstroem, α = 91.12(3), β = 105.36(3), γ = 111.39(3)deg, and Z = 2; R = 0.046 for 4 704 observed reflections.The influence of NH3, NHEt2, and H2NNH2 on the reactivity of cis- with monosubstituted acetylenes is discussed.

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