15693-82-0Relevant academic research and scientific papers
Reactions of a phosphoranide platinum(II) complex with nucleophilic and electrophilic reagents and the X-ray crystal structures of (η2-cyclenP)Pt[Co(CO)4]PPh3 and (η2-cyclenP)Pt(I)PPh3
Khasnis, Dilip V.,Lattman, Michael,Siriwardane, Upali
, p. 2594 - 2600 (2008/10/08)
The reactions of the phosphoranide-containing complex (η2-cyclenP)Pt(Cl)PPh3 (1) with a variety of nucleophiles and electrophiles have been studied. These reactions demonstrate the remarkable range and selectivity of this complex. With the anionic nucleophiles Co(CO)4-, SMe-, I-, and Br-, the corresponding chloride-substituted derivatives are formed, (η2-cyclenP)PtLPPh3, where L = Co(CO)4 (5), SMe (6), I (7), and Br (8). The neutral, potentially bidentate, donor dppm leads to PPh3 substitution to give (η2-cyclenP)Pt(CI)dppm (9), where only one of the phosphorus sites of dppm is bound to the platinum. The electrophiles MeI and n-BuBr also lead to 7 and 8. However, the reaction of MeO3SCF3 with 1 led to [(η2-MecyclenP)Pt(Cl)PPh3]O3SCF3 (10), where the platinum-bound nitrogen is methylated and the P-N bond is cleaved. This suggests that the alkyl halide reactions may proceed through such an intermediate, rather than the usual oxidative-addition/reductive-elimination path. The reaction of 1 with HC≡CPh and NaBPh4 leads to the σ-bonded alkyne complex [(η2-HcyclenP)Pt(C≡CPh)PPh3]BPh4 (11), where both P-N bond cleavage and chloride substitution has occurred. Reaction of 5 and Me3SiI leads to 7 and Me3SiCo(CO)4. The X-ray crystal structures of 5 and 7 were obtained and show extremely long Pt-Co and Pt-I bonds, respectively. X-ray data: C30H31N4O4P2CoPt (5, triclinic, space group P1 a = 10.374 (4) ?, b = 10.857 (6) ?, c = 16.086 (9) ?, α = 78.93 (4)°, β = 83.31 (4)°, γ = 61.93 (3)°, Z = 2, R = 0.059, Rw = 0.060; C26H31N4P2IPt (7), monoclinic, space group P21/c, a = 11.939 (5) ?, b = 14.446 (5) ?, c = 15.407 (9) ?, β = 92.80 (4)°, Z = 4, R = 0.053, Rw = 0.064.
