Insertion of CO2-like molecules into the platinum–nitrogen bond of [Pt(PPh3)2(PhNO)]: the X-ray structures of [Pt{ON(Ph)C(NPh)S}(PPh3)2] and [Pt{ON(Ph)C(O)NPh}(PPh3)2]

Abstract

The X-ray structure determination of the insertion product of [Pt(PPh₃)₂(PhNO)](1) with PhNCS, [[graphic omitted]}(PPh₃)₂][monoclinic, space group P2₁/n, with a= 17.779(7), b= 15.297(3), c= 17.951(4)Å, β= 109.49(2)°, and Z= 4; R= 0.036 for 4317 reflections with I 3σ(I)] has now confirmed the previously proposed structure for this compound. However, the X-ray structure determination of the insertion product with PhNCO, [[graphic omitted]Ph}(PPh₃)₂][orthorhombic, space group Pbca, with a= 25.303(8), b= 19.462(6), c= 17.451(5)Å, and Z= 8; R= 0.075 for 2001 reflections with I 3σ(I)], while having confirmed that a C–N bond is formed within the co-ordination sphere of the metal, has shown that the entering molecule is bonded to platinum via nitrogen and not oxygen, as previously suggested. The difference in reactivity of PhNCS and PhNCO with complex (1) is discussed.