Transition metal–carbon bonds. Part 49. The action of amines on cis-[PtCl 2 (PPr n 3 )(C 3 H 4 )]: crystal structures of the complexes [PtCl(PPr n 3 ){C(CH 2 )CH 2 NHBu t }](four-membered ring) and [Pt 2 Cl 2 (PPr n 3 ) 2 {C(CH 2 )CH 2 NHMe} 2 ](eight-membered ring)
1981; Royal Society of Chemistry; Issue: 2 Linguagem: Inglês
10.1039/dt9810000575
ISSN2050-5671
AutoresJohn R. Briggs, Christopher Crocker, Walter S. McDonald, Bernard L. Shaw,
Tópico(s)Asymmetric Hydrogenation and Catalysis
ResumoAddition of NR3(R = Me or Et) to the allene complex cis-[PtCl2(PPrn3)(C3H4)] rapidly gives the zwitterionic alkenyl complexes [PtCl2(PPrn3){C(CH2)CH2NR3}]. Addition of NH2But to the allene complex at or below –20° C gives an analogous complex, viz.[PtCl2(PPrn3){C(CH2)CH2NH2But}], but this with base, i.e. an excess of NH2But or preferably Na[OPri], immediately cyclizes to give [[graphic omitted]HBut}](5) the crystal structure of which has been determined and shown to contain a four-membered ring. Treatment of the allene complex with an excess of methylamine gives [[graphic omitted]HMe}2](6a) the crystal structure of which has also been determined and shown to contain an eight-membered ring. Benzylamine gives an analogous complex. Proton, 31P, and 195Pt n.m.r. data are given and discussed, as are i.r. data. Crystals of (5) are monoclinic, space group C2/c, with a= 19.653(3), b= 11.538(2), c= 18.785(2)Å, β= 107.10(1)°, and Z= 8; R= 0.036 for 2 300 independent reflections. The complex (6a) is monoclinic, space group P21/n, with a= 11.315(3), b= 13.782(2), c= 11.385(3)Å, β= 100.76(2)°, and Z= 2; R= 0.032 for 2 083 independent reflections.
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