FURTHER INVESTIGATIONS OF THE REACTIVITY OF ETA-2-BONDED NITROSO COMPLEXES OF PLATINUM - THE CRYSTAL-STRUCTURE OF PT(PPH3)2(PHNO)

The crystal structure of Pt(PPh3)2(PhNO) (I) has been determined. This is the first example of a structure determination for a monomeric complex of a metal in a low oxidation state and bearing an η2-bonded nitroso ligand. Compound I crystallizes in the monoclinic space group P21/c (no.14) with a 14.228(4), b 13.914(3), c 17.855(4) Å, β 100.31 (2)°, V 3478(3) Å3 and Z = 4. Final R and Rw indices are 0.026 and 0.030 for 3609 observed reflections (I ≥ 3 σ(I)). The new complexes Pt(PPh3)2(RNO) (R = But (II), CF3 (III)) have been synthesized and their reactions with CO2, CS2, PhNCO, PhNCS, CO, alkenes and dimethyl acetylenedicarboxylate have been investigated and compared with those of the previously studied compound I. Preliminary observations on the synthesis and reactivity of Pd(PPh3)2(CF3NO) (IV) are also reported.