40. "Platinum(II) Phosphido Complexes as Metalloligands. Structural and Spectroscopic Consequences of Conversion from Terminal to Bridging Coordination." Scriban, C.; Wicht, D. K.; Glueck, D. S.; Zakharov, L. N.; Golen, J. A.; Rheingold, A. L. Organometallics 2006, 25, 3370-3378.
Abstract Treatment of the terminal phosphido complexes Pt(dppe)(Me)(PPh(R)) (R = Ph (1), R = 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), R = 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 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 cation 8, while oxidation of 6 with H2O2 gave the crystallographically characterized phosphido oxide complex Pt(dppe)(Me)(P(O)Ph(i-Bu)) (12).