Organometallics, 25 (14), 3370 -3378, 2006

Comment P-31 NMR and p31-pt J-coupling

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

Corina Scriban, Denyce K. Wicht, David S. Glueck, Lev N. Zakharov, James A. Golen, and Arnold L. Rheingold

Abstract:

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 phosphido complexes [(Pt(dppe)(Me))₂(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 (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)]⁺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).