Bond complexes with phosphine

Mdssbauer spectra of bonding and structure in, 15 184-187 reactions with diborane, 16 213 stabilization of, 5 17, 18-19 cyanates, 17 297, 298 cyanide complexes of, 8 143-144 cyclometallated bipyridine complex, 30 76 diazene complexes, 27 231-232 dinitrogen complexes, 27 215, 217 diphosphine complexes of, 14 208-219 dithiocarbamates, 23 253-254 -1,2-dithiolene complexes, 22 323-327 hydrogen bonding, 22 327 halide complexes with phosphine, etc., 6 25 hexaflouride, structure, 27 104 hydride complexes, 20 235, 248-281, see also Transition metal-hydride complexes... 

Metal-Metal Bond Making and Breaking in Binuclear Complexes with Phosphine Bridging Ligands... 

Although a number of iron complexes having phosphine ligands have been prepared, of particular interest are a series of iron diphosphine complexes. They have been extensively studied because the iron(O) complexes generated from them are capable of activating C—H bonds or small molecules (Scheme 10.13). In this section, iron complexes with phosphines are briefly reviewed from the viewpoint of the chemistry of zero-valent iron complexes. Other recommended reading is given in ref 5. 

Further, in contrast to heterogeneous catalysis, where scattering of deuterium throughout the molecule usually results, selective addition of D2 to a double bond occurs. Finally, asymmetric hydrogenation has been achieved by use of complexes with phosphines that are optically active either at the phosphorus atom or at a carbon atom on the group attached to P.53 The mechanism of reduction probably involves the following steps ... 

Attention should be paid to the fact that the ratio of Pd and phosphine ligand in active catalysts is crucial for determining the reaction paths. It is believed that dba is displaced completely with phosphines when Pd2(dba)3 is mixed with phosphines in solution. However the displacement is not eom-plcte[16]. Also, it should be considered that dba itself is a monodentate alkene ligand, and it may inhibit the coordination of a sterically hindered olefinic bond in substrates. In such a case, no reaction takes place, and it is recommended to prepare Pd(0) catalysts by the reaction of Pd(OAc)2 with a definite amount of phosphinesflO]. In this way a coordinatively unsaturated Pd(0) catalyst can be generated. Preparation of Pd3(tbaa)3 tbaa == tribenzylidene-acetylacetone) was reported[17], but the complex actually obtained was Pd(dba)2[l8],... 

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