TY - JOUR
T1 - Conversion of acetonitrile into acetamide in the co-ordination spheres of cis- and trans-MII(amine)2 (M = Pt or Pd). Solution and crystal structural studies
AU - Erxleben, Andrea
AU - Mutikainen, Iipo
AU - Lippert, Bernhard
PY - 1994
Y1 - 1994
N2 - The preparation and solution behaviour of mono- and bis-acetonitrile complexes of cis-[Pt(NH3)2Cl2], [Pt(en)Cl2] (en = ethane-1,2-diamine) and trans-[Pt(NH3)2Cl2] has been investigated. The nitrile complexes are hydrolysed to acetamidate, acetamidate-bridged and mixed acetamidate-acetonitrile species. It is shown that an essential feature of monomeric acetamidate complexes with cis configuration is their tendency to dimerize to dinuclear platinum compounds having bridging amidate ligands. The resulting dinners undergoa facile head-to-tail to head-to-head rearrangement without any detectable intermediate. Solution studies of the mononitrile complex trans-[Pt(NH3)2(MeCN)(OH)]+ at around neutral pH reveal the formation of trans-[Pt(NH3)2(MeCN)(NHCOMe)]+, suggesting a preceding ligand exchange. The reactions of platinum with MeCN are compared with those of the kinetically labile palladium. The nitrile complex cis-[Pt(NH3)2(MeCN)Cl]ClO4 and the mixed-ligand complex trans-[Pt(NH3)2(MeCN)(NHCOMe)]ClO4 were characterized by X-ray crystallography: cis-[Pt(NH3)2-(MeCN)Cl]ClO4, monoclinic, space group P21/c, a = 10.618(10), b = 10.625(8), c = 9.176(7) Å, β = 111.20(6)°, Z = 4; trans-[Pt(NH3)2(MeCN)(NHCOMe)]ClO4, monoclinic, space group P21/c, a = 8.601 (6), b = 19.508(19), c = 7.625(4) Å, β = 11 5.29(5)°, Z = 4.
AB - The preparation and solution behaviour of mono- and bis-acetonitrile complexes of cis-[Pt(NH3)2Cl2], [Pt(en)Cl2] (en = ethane-1,2-diamine) and trans-[Pt(NH3)2Cl2] has been investigated. The nitrile complexes are hydrolysed to acetamidate, acetamidate-bridged and mixed acetamidate-acetonitrile species. It is shown that an essential feature of monomeric acetamidate complexes with cis configuration is their tendency to dimerize to dinuclear platinum compounds having bridging amidate ligands. The resulting dinners undergoa facile head-to-tail to head-to-head rearrangement without any detectable intermediate. Solution studies of the mononitrile complex trans-[Pt(NH3)2(MeCN)(OH)]+ at around neutral pH reveal the formation of trans-[Pt(NH3)2(MeCN)(NHCOMe)]+, suggesting a preceding ligand exchange. The reactions of platinum with MeCN are compared with those of the kinetically labile palladium. The nitrile complex cis-[Pt(NH3)2(MeCN)Cl]ClO4 and the mixed-ligand complex trans-[Pt(NH3)2(MeCN)(NHCOMe)]ClO4 were characterized by X-ray crystallography: cis-[Pt(NH3)2-(MeCN)Cl]ClO4, monoclinic, space group P21/c, a = 10.618(10), b = 10.625(8), c = 9.176(7) Å, β = 111.20(6)°, Z = 4; trans-[Pt(NH3)2(MeCN)(NHCOMe)]ClO4, monoclinic, space group P21/c, a = 8.601 (6), b = 19.508(19), c = 7.625(4) Å, β = 11 5.29(5)°, Z = 4.
UR - https://www.scopus.com/pages/publications/37049073177
U2 - 10.1039/DT9940003667
DO - 10.1039/DT9940003667
M3 - Article
AN - SCOPUS:37049073177
SN - 1472-7773
SP - 3667
EP - 3675
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 24
ER -