Phosphino derivative

The ligands are phosphino derivatives of Ai-/ ri-butoxycatbonyl pyrrohdine, BPPM and BCPM ... 

Comprehensive studies of molecular structures of neutral NHPs have been in particular performed for P-halogen, P-amino, and P-phosphino derivatives in... 

Homochiral pyridyl, bipyridyl, and phosphino derivatives of 2,2-dimethyl-1,3-dioxolane (113)-(115) were prepared from T-(+)-tartrate. These compounds were assessed in metal-catalyzed asymmetric hydroformylation of styrene enantioselectivity was generally low.342... 

The crystal structures of the AuI/Fe11 complexes have been determined by X-ray diffraction methods showing a typical linear environment for the gold(I) center and none of them display intramolecular Au- Fe interactions (see Fig. 8). The phosphino derivative does not display intermolecular Au- -Au interactions either (the shortest gold-gold distance is 5.560 A), but the lattice shows F- -F (2.858 A) and F- -H (2.55 and 2.60 A) contacts. In contrast, ferrocenylpyridine complex molecules are associated into pairs across inversion centers via a weak intermolecular Au- -Au interaction of 3.301(2) A, similar to that observed in the case of the (thiophenylmethyl)diphenylpho-sphine derivative [ (C6F5)Au 2 p.-PPh2C(=S)N(H)Me described above (Au- -Au 3.2712(5) A).34... 

Table 6 Mono- and bis(arene)/phosphino derivatives of early transition metals prepared by metal vapor synthesis...

However, when the same reaction is performed with camphcne. two main products are formed, the phosphetane 15 and the noncyclic chloro(methyl)phosphino derivative 16 15 is obtained in the optically active form ([a]D —9.4, ee not given), while 16 is racemic13. 

Although a terminal phosphido group is not available in phosphino derivatives 2(Nb, Ta), they behave as metalloligands towards unsaturated organometallic fragments also giving rise to dibridged complexes Il(Ta, Nb) (Fig. 

The rates of insertion of ethylene into Pd-alkyl and Pd-acyl bonds have been evaluated for this type of systems, in particular [Pd(R)(C2H4)(L-L)]+ (R = alkyl, acyl L-L = phen, 1,3-diphenylphosphinopropane) [117,118], Lower activation barriers for the acyl complexes were consistently found with AAG (alkyl-acyl) about 2 kcal for the phen complexes and 4 kcal for the phosphino derivatives. Insertion barriers for CO insertion into the Pd-alkyl bond are even lower, making the alternating copolymerization of alkenes and CO possible and almost flawless (a perfect sequence of CO insertion into M-alkyl and alkene insertion into M-acyl with absence of alkene insertion into M-alkyl) [119]. 

When the phosphino derivatives 82, 83 were hydroformylated at higher temperatnres (90°C) alcohols were formed as a consequence of consecutive hydroformylation-reduction. This is an interesting result since alcohols are not usually obtained with modified rhodium catalysts. 

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