Platinum(II) Phosphido Complexes as Metalloligands. Structural and Spectroscopic Consequences of Conversion from Terminal to Bridging Coordination

Treatment of the terminal phosphido complexes Pt(dppe)(Me)(PPh(R)) (R = Ph (1), i-Bu (6)) with
Pt(dppe)(Me)(OTf) gave the cationic μ-phosphido complexes [(Pt(dppe)(Me))2(μ-PPh(R))][OTf] (R =
Ph (7), i-Bu (8)). Similarly, Pt((R,R)-Me-Duphos)(Me)(PPh(i-Bu)) (10) was converted to [(Pt((R,R)-Me-Duphos)(Me))2(μ-PPh(i-Bu))][OTf] (11). A fluxional process in 8 and 11, presumably involving hindered
rotation about the Pt−PPh(i-Bu) bonds, was observed by NMR spectroscopy; it resulted in two
diastereomers for 8 and four for 11 at low temperature. Coordination of the metalloligand 10 to the
[Pt((R,R)-Me-Duphos)(Me)]+ fragment, yielding 11, resulted in structural changes at the Pt−phosphido
group, whose geometry changed from distorted pyramidal to tetrahedral. Decomposition of 6 also gave
the cation 8, while oxidation of 6 with H2O2 gave the crystallographically characterized phosphido oxide
complex Pt(dppe)(Me)(P(O)Ph(i-Bu)) (12).