Complexes of trimethylphosphine

Complexes of trimethylphosphine (cone angle 118°) [115]. Syntheses are shown in Figure 2.63. The rhodium(III) complexes can be made by the usual routes or by oxidation of rhodium(I) complexes. Note that in contrast with the bulkier PPh3, refluxing RhCl3 with PMe3 does not result in reduction. 

Figure 2.63 Syntheses and interrelationships between rhodium complexes of trimethylphosphine.

The condensation of pyridine and trimethylphosphine complexes of borabenzene with dimethyl acetylenedicar-boxylate leads to the corresponding 1-borabarrelene complexes 146 and 147 (Scheme 58). 

In the presence of trimethylphosphine or 4-dimethylaminopyridine, titanocene vinylimido complexes 84 are produced by treating the in situ generated titanocene-methy-... 

Torsional barriers for trimethylphosphine derivatives (63) have been obtained from Raman spectra.56 Vibrational spectra for the uranyl nitrate complex of (63a) have been published.66 Complexes of triarylphosphine derivatives (64) with iodine,67 and of (64b) with metal halides,68 have been the subject of thermodynamic67 and spectroscopic67 68 study. 

Scheme 7.2 Reactions of the surface 7t-allyl rhodium siloxide complex with trimethylphosphine.

For this complex, molecular chemistry does not adequately model the surface reactivity and the latter is strongly influenced by the presence of surface hydroxyl groups [22]. The organometallic fragments immobilized on silica have been reacted with trimethylphosphine to afford different silica-supported phosphine complexes of rhodium. The course of the reaction depends strongly on the hydroxyl content of the silica surface [23] (Scheme 7.2). 

Fig. 6.25 ORTEP diagram of complex containing trimethylphosphine and ntirosohenzenc ligands, and two platinum atoms. Note the differences in the sizes of the thermal ellipsoids for C, N. and Pt. For a discussion of the types of bonding in this complex, sec Chapter 12. [From Packeli, D. L, Troglcr, W. C. Rhcingold, A. L. Inory. Chcm. IPS , 26, 4309. Reproduced with permission. ...

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